Pest control agents

ABSTRACT

Disclosed is a composition for use as a pest control agent, comprising a compound represented by formula (I) or an agriculturally and horticulturally acceptable salt thereof as active ingredient and an agriculturally and horticulturally acceptable carrier:

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention relates to a composition for use as a pest controlagent comprising a pyripyropene derivative as active ingredient.

2. Background Art

Pyripyropene A has inhibitory activity against ACAT (acyl-CoA:cholesterol acyltransferase) and is expected to be applied, for example,to the treatment of diseases induced by cholesterol accumulation, asdescribed in Japanese Patent No. 2993767 (Japanese Patent Laid-OpenPublication No. 360895/1992) and Journal of Antibiotics (1993), 46(7),1168-9.

Further, pyripyropene analogues and derivatives and ACAT inhibitoryactivity thereof are described in Journal of Society of SyntheticOrganic Chemistry, Japan (1998), Vol. 56, No. 6, pp. 478-488, WO94/09417, Japanese Patent Laid-Open Publication No. 184158/1994,Japanese Patent Laid-Open Publication No. 239385/1996, Japanese PatentLaid-Open Publication No. 259569/1996, Japanese Patent Laid-OpenPublication No. 269062/1996, Japanese Patent Laid-Open Publication No.269063/1996, Japanese Patent Laid-Open Publication No. 269064/1996,Japanese Patent Laid-Open Publication No. 269065/1996, Japanese PatentLaid-Open Publication No. 269066/1996, Japanese Patent Laid-OpenPublication No. 291164/1996, and Journal of Antibiotics (1997), 50(3),229-36.

Furthermore, Applied and Environmental Microbiology (1996), 61(12),4429-35 describes that pyripyropene A has insecticidal activity againstlarvae of Helicoverpa zea. Furthermore, WO 2004/060065 describes thatpyripyropene A has insecticidal activity against Plutella xylostella Llarvae and Tenebrio molitor L. In these documents, however, there is nospecific description on insecticidal activity of pyripyropene A againstother pests.

Further, none of the above documents describes insecticidal activity ofpyripyropene analogues and derivatives.

Up to now, many compounds having insecticidal activity have beenreported and have been used as pest control agents. However, thepresence of insect species, which are resistant to or can be hardlycontrolled by these compounds, has posed a problem. Accordingly, thedevelopment of a novel pest control agent having excellent insectidalactivity has still been desired.

SUMMARY OF THE INVENTION

The present inventors have now found that pyripyropene derivativesrepresented by formula (I) have significant insecticidal activity.

The present inventors further found that pyripyropene A and itsderivatives represented by formula (Ia) have significant insecticidalactivity against hemipteran pests.

Furthermore, the present inventors have found novel pyripyropenederivatives represented by formula (Ib) having significant insecticidalactivity.

The present invention has been made based on such finding.

Accordingly, an object of the present invention is to provide acomposition useful as a pest control agent, that comprises apyripyropene derivative having significant insecticidal activity asactive ingredient and can reliably exhibit the contemplated effect andcan be used safely. Another object of the present invention is toprovide a hemipteran pest control agent that comprises pyripyropene Aand its derivative as active ingredient and can reliably exhibit thecontemplated effect and can be used safely. A further object of thepresent invention is to provide a novel pyripyropene derivative havingsignificant insecticidal activity.

According to one aspect of the present invention, there is provided acomposition for use as a pest control agent, comprising a compoundrepresented by formula (I) or an agriculturally and horticulturallyacceptable salt thereof as active ingredient and an agriculturally andhorticulturally acceptable carrier:

wherein

-   -   Het₁ represents optionally substituted 3-pyridyl,    -   R₁ represents hydroxy,        -   optionally substituted C₁₋₆ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted C₂₋₆ alkynylcarbonyloxy,        -   optionally substituted C₁₋₆ alkyloxy,        -   optionally substituted C₂₋₆ alkenyloxy,        -   optionally substituted C₂₋₆ alkynyloxy,        -   optionally substituted benzyloxy, or        -   oxo in the absence of a hydrogen atom at the 13-position,        -   or    -   the bond between 5-position and 13-position represents a double        bond in the absence of R₁ and a hydrogen atom at the 5-position,        -   R₂ represents hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted C₂₋₆ alkynylcarbonyloxy,        -   optionally substituted benzoyloxy, or        -   optionally substituted C₁₋₆ alkylsulfonyloxy,        -   R₃ represents a hydrogen atom,        -   hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted C₂₋₆ alkynylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted C₁₋₆ alkylsulfonyloxy,        -   optionally substituted benzenesulfonyloxy, or        -   optionally substituted five- or six-membered heterocyclic            thiocarbonyloxy, or    -   R₂ and R₃ together represent —O—CR₂′R₃—O— wherein R₂′ and R₃′,        which may be the same or different, represent a hydrogen atom,        C₁₋₆ alkyl, C₁₋₆ alkyloxy, C₂₋₆ alkenyl, optionally substituted        phenyl, or optionally substituted benzyl, or R₂′ and R₃′        together represent oxo or C₂₋₆ alkylene, and    -   R₄ represents a hydrogen atom,        -   hydroxyl;        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted C₂₋₆ alkynylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted C₁₋₆ alkylsulfonyloxy,        -   optionally substituted benzenesulfonyloxy,        -   optionally substituted benzyloxy,        -   optionally substituted C₁₋₆ alkyloxy,        -   optionally substituted C₂₋₆ alkenyloxy,        -   optionally substituted C₂₋₆ alkynyloxy,        -   C₁₋₆ alkyloxy-C₁₋₆ alkyloxy,        -   C₁₋₆ alkylthio-C₁₋₆ alkyloxy,        -   C₁₋₆ alkyloxy-C₁₋₆ alkyloxy-C₁₋₆ alkyloxy,        -   optionally substituted C₁₋₆ alkyloxycarbonyloxy,        -   optionally substituted C₁₋₆ alkylamincoarbonyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic oxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic carbonyloxy,        -   optionally substituted thieno[3,2-b]pyridylcarbonyloxy,        -   optionally substituted 1H-indolylcarbonyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic thiocarbonyloxy, or        -   oxo in the absence of a hydrogen atom at the 7-position,        -   provided that        -   a compound wherein        -   Het₁ represents 3-pyridyl,        -   R₁ represents hydroxyl, and        -   all of R₂, R₃, and R₄ represent acetyloxy,            is excluded.

Further, according to another aspect of the present invention, there isprovided a composition for use as a a hemipteran pest control agent,comprising a compound represented by formula (Ia) or an agriculturallyand horticulturally acceptable salt thereof as active ingredient and anagriculturally and horticulturally acceptable carrier:

wherein

-   -   Het₂ represents optionally substituted 3-pyridyl,    -   R₁₁ represents hydroxyl,        -   optionally substituted C₁₋₆ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted C₂₋₆ alkynylcarbonyloxy,        -   optionally substituted C₁₋₆ alkyloxy,        -   optionally substituted C₂₋₆ alkenyloxy,        -   optionally substituted C₂₋₆ alkynyloxy,        -   optionally substituted benzyloxy, or        -   oxo in the absence of a hydrogen atom at the 13-position,    -   or    -   the bond between 5-position and 13-position represents a double        bond in the absence of R₁₁ and a hydrogen atom at the        5-position,    -   R₁₂ represents hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted C₂₋₆ alkynylcarbonyloxy,        -   optionally substituted benzoyloxy, or        -   optionally substituted C₁₋₆ alkylsulfonyloxy,    -   R₁₃ represents a hydrogen atom,        -   hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted C₂₋₆ alkynylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted C₁₋₆ alkylsulfonyloxy,        -   optionally substituted benzenesulfonyloxy, or        -   optionally substituted five- or six-membered heterocyclic            thiocarbonyloxy, or    -   R₁₂ and R₁₃ together represent —O—CR₁₂′R₁₃′—O— wherein R₁₂′ and        R₁₃′, which may be the same or different, represent a hydrogen        atom, C₁₋₆ alkyl, C₁₋₆ alkyloxy, C₂₋₆ alkenyl, optionally        substituted phenyl, or optionally substituted benzyl, or R₁₂′        and R₁₃′ together represent oxo or C₂₋₆ alkylene, and    -   R₁₄ represents a hydrogen atom,        -   hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted C₂₋₆ alkynylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted C₁₋₆ alkylsulfonyloxy,        -   optionally substituted benzenesulfonyloxy,        -   optionally substituted benzyloxy,        -   optionally substituted C₁₋₆ alkyloxy,        -   optionally substituted C₂₋₆ alkenyloxy,        -   optionally substituted C₂₋₆ alkynyloxy,        -   C₁₋₆ alkyloxy-C₁₋₆ alkyloxy,        -   C₁₋₆ alkylthio-C₁₋₆ alkyloxy,        -   C₁₋₆ alkyloxy-C₁₋₆ alkyloxy-C₁₋₆ alkyloxy,        -   optionally substituted C₁₋₆ alkyloxycarbonyloxy,        -   optionally substituted C₁₋₆ alkylaminocarbonyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic oxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic carbonyloxy,        -   optionally substituted thieno[3,2-b]pyridylcarbonyloxy,        -   optionally substituted 1H-indolylcarbonyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic thiocarbonyloxy, or        -   oxo in the absence of a hydrogen atom at the 7-position.

Further, the pyripyropene derivative according to the present inventioncomprises a compound represented by formula (Ib) or an agriculturallyand horticulturally acceptable salt thereof:

wherein

-   -   Het₁ represents 3-pyridyl,    -   R₁ represents hydroxyl,    -   R₂ and R₃ represent propionyloxy or optionally substituted        cyclic C₃₋₆ alkylcarbonyloxy, and    -   R₄ represents hydroxyl,        -   optionally substituted cyclic C₃₋₆ alkylcarbonyloxy,        -   optionally substituted benzoyloxy, or        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic carbonyloxy.

The pyripyropene derivatives represented by formula (I) or formula (Ib)according to the present invention have excellent control effect againstagricultural and horticultural pests, sanitary pests, parasites ofanimals, stored grain pests, clothing pests, and house pests and acompositions comprising the pyripyropene derivatives as activeingredient can be advantageously utilized as a novel pest control agent.

Further it is surprising that, among the compounds represented byformula (Ia), pyripyropene A has excellent control effect againsthemipteran pests. Accordingly, a composition according to the presentinvention comprising the compounds represented by formula (Ia) includingpyripyropene A, can be advantageously utilized particularly a hemipteranpest control agent.

DETAILED DESCRIPTION OF THE INVENTION

The term “halogen” as used herein means fluorine, chlorine, bromine, oriodine, preferably fluorine, chlorine, or bromine.

The terms “alkyl,” “alkenyl,” and “alkynyl” as used herein as a group ora part of a group respectively mean alkyl, alkenyl, and alkynyl that thegroup is of a straight chain, branched chain, or cyclic type or a typeof a combination thereof unless otherwise specified. Further, forexample, “C₁₋₆” in “C₁₋₆ alkyl” as used herein as a group or a part of agroup means that the number of carbon atoms In the alkyl group is 1 to6. Further, in the case of cyclic alkyl, the number of carbon atoms isat least three.

The term “heterocyclic ring” as used herein means a heterocyclic ringcontaining one or more, preferably one to four, heteroatoms, which maybe the same or different, selected from the group consisting ofnitrogen, oxygen, and sulfur atoms. Further, the expression “optionallysubstituted” alkyl as used herein means that one or more hydrogen atomson the alkyl group may be substituted by one or more substituents whichmay be the same or different. It will be apparent to a person havingordinary skill in the art that the maximum number of substituents may bedetermined depending upon the number of substitutable hydrogen atoms onthe alkyl group. This is true of functional groups other than the alkylgroup.

3-Pyridyl represented by Het₁ and Het₂ is optionally substituted, andsubstituents include halogen atoms, C₁₋₄ alkyl, C₁₋₄ alkyloxy, nitro,cyano, formyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,trifluoromethylsulfinyl, trifluoromethylsulfonyl, acetyl, and acetyloxy.Preferred are halogen atoms and trifluoromethyl. A chlorine atom andtrifluoromethyl are more preferred.

“C₁₋₆ alkylcarbonyloxy” represented by R₁ and R₁₁ is optionallysubstituted, and substituents include halogen atoms, cyano, phenyl,trifluoromethoxy, and trifluoromethylthio.

“C₁₋₁₈ alkylcarbonyloxy” represented by R₂, R₃ and R₄, and R₁₂, R₁₃ andR₁₄ is preferably C₁₋₆ alkylcarbonyloxy, more preferably propionyloxy orcyclic C₃₋₆ alkylcarbonyloxy. The alkylcarbonyloxy group is optionallysubstituted, and substituents include halogen atoms, cyano, cyclicC₃₋₆alkyl, phenyl, trifluoromethoxy, trifluoromethylthio, pyridyl, andpyridylthio. More preferred are halogen atoms, cyclic C₃₋₆ alkyl, andpyridyl.

“C₂₋₆ alkenylcarbonyloxy” represented by R₁, R₂, R₃ and R₄, and R₁₁,R₁₂, R₁₃ and R₁₄ is optionally substituted, and substituents includehalogen atoms, cyano, phenyl, trifluoromethoxy, and trifluoromethylthio.

“C₂₋₆ alkynylcarbonyloxy” represented by R₁, R₂, R₃ and R₄, and R₁₁,R₁₂, R₁₃ and R₁₄ is optionally substituted, and substituents includehalogen atoms, cyano, phenyl, trifluoromethoxy, and trifluoromethylthio.

“C₁₋₆ alkyloxy” represented by R₁ and R₄, and R₁₁ and R₁₄ is optionallysubstituted, and substituents include halogen atoms; cyano; phenyl;trifluoromethoxy; trifluoromethylthio; C₁₋₆ alkylcarbonyl optionallysubstituted by a halogen atom; and C₁₋₆ alkylcarbonyloxy optionallysubstituted by a halogen atom.

“C₂₋₆ alkenyloxy” represented by R₁ and R₄, and R₁₁ and R₁₄ isoptionally substituted, and substituents include halogen atoms; cyano;phenyl; trifluoromethoxy; trifluoromethylthio; C₁₋₆ alkylcarbonyloptionally substituted by a halogen atom; and C₁₋₆ alkylcarbonyloxyoptionally substituted by a halogen atom.

“C₂₋₆ alkynyloxy” represented by R₁ and R₄, and R₁₁ and R₁₄ isoptionally substituted, and substituents include halogen atoms; cyano;phenyl; trifluoromethoxy; trifluoromethylthio; C₁₋₆ alkylcarbonyloptionally substituted by a halogen atom; and C₁₋₆ alkylcarbonyloxyoptionally substituted by a halogen atom.

Phenyl in “benzyloxy” represented by R₁ and R₄, and R₁₁ and R₁₄ isoptionally substituted, and substituents include halogen atoms; C₁₋₆alkyloxy optionally substituted by a halogen atom: C₁₋₆ alkyl optionallysubstituted by a halogen atom; C₁₋ ₆ alkylcarbonyl optionallysubstituted by a halogen atom; C₁₋₆ alkylcarbonyloxy optionallysubstituted by a halogen atom; C₁₋₆ alkylcarbonylamino optionallysubstituted by a halogen atom; C₁₋₆ alkylaminocarbonyloxy optionallysubstituted by a halogen atom; C₁₋₆ alkylaminocarbonyl optionallysubstituted by a halogen atom; C₁₋₆ alkylsulfonyloxy optionallysubstituted by a halogen atom; C₁₋₆ alkylthio optionally substituted bya halogen atom; C₁₋₆ alkylsulfinyl optionally substituted by a halogenatom; C₁₋₆ alkylsulfonyl optionally substituted by a halogen atom,cyano; formyl; azide; guanidyl; group —C(═NH)—NH₂; and group—CH═N—O—CH₃.

Phenyl in “benzoyloxy” represented by R₂, R₃ and R₄, and R₁₂, R₁₃ andR₁₄ is optionally substituted, and substituents include halogen atoms;C₁₋₆ alkyloxy optionally substituted by a halogen atom; C₁₋₆ alkyloptionally substituted by a halogen atom; C₁₋₆ alkylcarbonyl optionallysubstituted by a halogen atom; C₁₋₆ alkylcarbonyloxy optionallysubstituted by a halogen atom; C₁₋₆ alkylcarbonylamino optionallysubstituted by a halogen atom; C₁₋₆ alkylaminocarbonyloxy optionallysubstituted by a halogen atom; C₁₋₆ alkylaminocarbonyl optionallysubstituted by a halogen atom; C₁₋₆ alkylsulfonyloxy optionallysubstituted by a halogen atom; C₁₋₆ alkylthio optionally substituted bya halogen atom; C₁₋₆ alkylsulfinyl optionally substituted by a halogenatom; C₁₋₆ alkylsulfonyl optionally substituted by a halogen atom;cyano; nitro; formyl; azide, guanidyl; group —C(═NH)—NH₂; and group—CH═N—O—CH₃. Preferred are halogen atoms, C₁₋₆ alkyl substituted by ahalogen atom, cyano, and nitro.

Phenyl in “benzenesulfonyloxy” represented by R₃ and R₄, and R₁₃ and R₁₄is optionally substituted, and substituents include halogen atoms; C₁₋₆alkyloxy optionally substituted by a halogen atom; C₁₋₆ alkyl optionallysubstituted by a halogen atom; C₁₋₆ alkylcarbonyl optionally substitutedby a halogen atom; C₁₋₆ alkylcarbonyloxy optionally substituted by ahalogen atom; C₁₋₆ alkylcarbonylamino optionally substituted by ahalogen atom; C₁₋₆ alkylaminocarbonyloxy optionally substituted by ahalogen atom; C₁₋₆ alkylaminocarbonyl optionally substituted by ahalogen atom; C₁₋₆ alkylsulfonyloxy optionally substituted by a halogenatom: C₁₋₆ alkylthio optionally substituted by a halogen atom; C₁₋₆alkylsulfinyl optionally substituted by a halogen atom; C₁₋₆alkylsulfonyl optionally substituted by a halogen atom; cyano; formyl;azide; guanidyl; group —C(═NH)—NH₂; and group —CH═H—O—CH₃.

“C₁₋₆ alkylsulfonyloxy” represented by R₂, R₃ and R₄, and R₁₂, R₁₃ andR₁₄ is optionally substituted, and substituents include halogen atoms,cyano, phenyl, trifluoromethoxy, and trifluoromethylthio.

“C₁₋₆ alkyloxycarbonyloxy” represented by R₄ and R₁₄ is optionallysubstituted, and substituents include halogen atoms, cyano, phenyl,trifluoromethoxy, and trifluoromethylthio.

“C₁₋₆ alkylaminocarbonyloxy” represented by R₄ and R₁₄ is optionallysubstituted, and substituents include halogen atoms, cyano, phenyl,trifluoromethoxy, and trifluoromethylthio.

“Phenyl” represented by R₂′ and R₃′, and R₁₂′ and R₁₃′ and phenyl in“benzyl” represented by R₂′ and R₃′, and R₁₂′ and R₁₃′ is optionallysubstituted, and substituents include halogen atoms, C₁₋₄ alkyl, C₁₋₄alkyloxy, nitro, cyano, formyl, trifluoromethoxy, acetyl, and acetyloxy.

“Saturated or unsaturated five- or six-membered heterocyclic ring” in“saturated or unsaturated five- or six-membered heterocyclicthiocarbonyloxy” represented by R₃ and R₁₃, and “saturated orunsaturated five- or six-membered heterocyclic oxy,” “saturated orunsaturated five- or six-membered heterocyclic carbonyloxy,” and“saturated or unsaturated five- or six-membered heterocyclicthiocarbonyloxy” represented by R₄ and R₁₄, is preferably, saturated orunsaturated five- or six-membered heterocyclic ring containing one tothree heteroatoms selected from the group consisting of nitrogen,oxygen, and sulfur atoms, more preferably, saturated or unsaturatedfive- or six-membered heterocyclic ring containing one or twoheteroatoms selected from the group consisting of nitrogen, oxygen, andsulfur atoms, more preferably, saturated or unsaturated five- orsix-membered heterocyclic ring containing one or two nitrogen atoms,saturated or unsaturated five- or six-membered heterocyclic ringcontaining one or two oxygen atoms, saturated or unsaturated five- orsix-membered heterocyclic ring containing one or two sulfur atoms,saturated or unsaturated five- or six-membered heterocyclic ringcontaining one nitrogen atom and one oxigen atom, or saturated orunsaturated five- or six-membered heterocyclic ring containing onenitrogen atom and one sulfur atom.

More specifically, examples of the “saturated or unsaturated five- orsix-membered heterocyclic ring” include thienyl, furyl, pyrrolyl,imidazolyl, pyrazolyl, isothiazoyl, isoxazolyl, thiazolyl, oxazolyl,pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, tetrahydropyranyl,piperidinyl, piperazinyl, morpholinyl, and mannosyl. Preferred arepyridyl, furanyl, thiazolyl, imidazolyl, tetrahydropyranyl, andmannosyl. More specific examples thereof include (2- or 3-)thienyl, (2-or 3-)furyl, (1-, 2- or 3-)pyrrolyl, (1-, 2-, 4- or 5-)imidazolyl, (1-,3-, 4- or 5-)pyrazolyl, (3-, 4- or 5-)isothiazoyl, (3-, 4- or5-)isoxazolyl, (2-, 4- or 5-)thiazolyl, (2-, 4- or 5-)oxazolyl, (2-, 3-or 4-)pyridyl or, (2-, 4-, 5- or 6-)pyrimidinyl, (2- or 3-)pyrazinyl,(3- or 4-)pyridazinyl, (2-, 3- or 4-)tetrahydropyranyl, (1-, 2-, 3- or4-)piperidinyl, (1-, 2- or 3-)piperazinyl, and (2-, 3- or4-)morpholinyl, preferably 3-pyridyl, 2-franyl, 5-thiazolyl,1-imidazolyl, 5-imidazolyl, and 2-tetrahydropyranyl, more preferably2-tetrahydropyranyl, 2-pyrazinyl, and 3-pyridyl, particularly preferably3-pyridyl.

The heterocyclic ring in the “saturated or unsaturated five- orsix-membered heterocyclic carbonyloxy” and “saturated or unsaturatedfive- or six-membered heterocyclic thiocarbonyloxy” and“thieno[3,2-b]pyridylcarbonyloxy” and “1H-indolylcarbonyloxy”represented by R₄ and R₁₄ are optionally substituted, and substituentsinclude halogen atoms, C₁₋₄ alkyl, C₁₋₄ alkyloxy, C₁₋₄ alkylthio, nitro,cyano, formyl, trifluoromethoxy, trifluoromethyl, trifluoromethylthio,trifluoromethylsulfinyl, trifluoromethylsulfonyl, acetyl, acetyloxy,benzoyl, and C₁₋₄ alkyloxycarbonyl. Preferred are halogen atoms, C₁₋₄alkyl, C₁₋₄ alkyloxy and trifluoromethyl.

The heterocyclic ring in the “saturated or unsaturated five- orsix-membered heterocyclic oxy” is optionally substituted, andsubstituents include hydroxyl, benzyloxy, a halogen atom, C₁₋₄ alkyl,C₁₋₄ alkyloxy, nitro, cyano, formyl, trifluoromethoxy, trifluoromethyl,trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl,acetyl, and acetyloxy. Preferred are hydroxyl and benzyloxy.

A Composition for Use as a Pest Control Agent, Comprising a CompoundRepresented by Formula (I)

According to a preferred embodiment of the present invention, in thecompound represented by formula (I), preferably, Het₁ represents3-pyridyl.

Further, according to a preferred embodiment of the present invention,in the compound represented by formula (I), R₁ represents hydroxyl, C₁₋₅alkylcarbonyloxy, C₁₋₃ alkyloxy, or benzyloxy, or oxo in the absence ofa hydrogen atom at the 13-position, or the bond between 5-position and13-position represents a double bond in the absence of R₁ and a hydrogenatom at the 5-position. More preferably, R₁ represents hydroxyl or C₁₋₆alkylcarbonyloxy, or the bond between 5-position and 13-positionrepresents a double bond in the absence of R₁ and a hydrogen atom at the5-position, still more preferably R₁ represents hydroxyl.

According to a preferred embodiment of the present invention, in thecompound represented by formula (1), R₂ represents hydroxyl, optionallysubstituted C₁₋₁₈ alkylcarbonyloxy, optionally substituted benzoyloxy,or C₁₋₃ alkylsulfonyloxy, more preferably optionally substituted C₁₋₁₈alkylcarbonyloxy, still more preferably optionally substituted C₁₋₆alkylcarbonyloxy, still more preferably straight chain or branched chainC₁₋₆ alkylcarbonyloxy (particularly propionyloxy) or optionallysubstituted cyclic C₃₋₆ alkylcarbonyloxy.

In a preferred embodiment of the present invention, in the compoundrepresented by formula (I), R₃ represents a hydrogen atom, hydroxyl,optionally substituted C₁₋₁₈ alkylcarbonyloxy, optionally substitutedbenzoyloxy, C₁₋₆ alkylsulfonyloxy, optionally substitutedbenzenesulfonyloxy, or saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, more preferably optionally substitutedC₁₋₆ alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, still more preferablyoptionally substituted C₁₋₆ alkylcarbonyloxy, still more preferablystraight chain or branched chain C₂₋₄ alkylcarbonyloxy (particularlypropionyloxy) or optionally substituted cyclic C₃₋₆ alkylcarbonyloxy.

According to a preferred embodiment of the present invention, in thecompound represented by formula (I), R₂ and R₃ together represent—O—CR₂′R₃′—O—, wherein R₂′ and R₃′, which may be the same or different,represent a hydrogen atom, C₁₋₆ alkyl, C₁₋₃ alkyloxy, C₂₋₃ alkenyl,benzyl, or optionally substituted phenyl, or R₂′ and R₃′ togetherrepresent oxo or C₂₋₆ alkylene. More preferably, R₂ and R₃ togetherrepresent —O—CR₂′R₃′—O—, wherein R₂′ and R₃′, which may be the same ordifferent, represent a hydrogen atom, C₁₋₆ alkyl, or optionallysubstituted phenyl, or R₂′ and R₃′ together represent oxo or C₂₋₆alkylene.

According to a preferred embodiment of the present invention, in thecompound represented by formula (I), R₄ represents a hydrogen atom,hydroxyl, optionally substituted C₁₋₁₈ alkylcarbonyloxy, C₂₋₆alkenylcarbonyloxy, C₂₋₆ alkynyl carbonyloxy, C₁₋₆ alkylsulfonyloxy,benzenesulfonyloxy, benzyloxy, C₁₋₃ alkyloxy, C₁₋₃ alkyloxy-C₁₋₃alkyloxy, C₁₋₃ alkylthio-C₁₋₃ alkyloxy, C₁₋₃ alkyloxy-C₁₋₃ alkyloxy-C₁₋₃alkyloxy, optionally substituted C₁₋₃ alkyloxycarbonyloxy, optionallysubstituted C₁₋₆ alkylaminocarbonyloxy, optionally substitutedbenzoyloxy, saturated or unsaturated five- or six-membered heterocyclicoxy, optionally substituted saturated or unsaturated five- orsix-membered heterocyclic carbonyloxy, optionally substitutedthieno[3,2-b]pyridylcarbonyloxy, optionally substituted1H-indolylcarbonyloxy, or saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atomat the 7-position, More preferably, R₄ represents hydroxyl, optionallysubstituted C₁₋₆ alkylcarbonyloxy, saturated or unsaturated five- orsix-membered heterocyclic oxy, optionally substituted benzoyloxy, C₁₋₃alkyloxy-C₁₋₃ alkyloxy, optionally substituted C₁₋₆alkylaminocarbonyloxy, optionally substituted saturated or unsaturatedfive- or six-membered heterocyclic carbonyloxy optionally substitutedthieno[3,2-b]pyridylcarbonyloxy, optionally substituted1H-indolylcarbonyloxy, or saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atomat the 7-position. Still more preferably, R₄ represents hydroxyl,optionally substituted C₁₋₆ alkylcarbonyloxy, saturated or unsaturatedfive- or six-membered heterocyclic oxy, optionally substitutedbenzoyloxy, optionally substituted saturated or unsaturated five- orsix-membered heterocyclic carbonyloxy, or saturated or unsaturated five-or six-membered heterocyclic thiocarbonyloxy. Still more preferably, R₄represents hydroxyl, straight chain or branched chain C₂₋₄alkylcarbonyloxy (particularly propionyloxy), optionally substitutedcyclic C₃₋₆ alkylcarbonyloxy, or optionally substituted saturated orunsaturated five- or six-membered heterocyclic carbonyloxy.

According to another preferred embodiment of the present invention, inthe compound represented by formula (I), Het₁ represents 3-pyridyl, R₁represents hydroxyl or C₁₋₆ alkylcarbonyloxy, or the bond between5-position and 13-position represents a double bond in the absence of R₁and a hydrogen atom at the 5-position, R₂ represents optionallysubstituted C₁₋₆ alkylcarbonyloxy, R₃ represents optionally substitutedC₁₋₆ alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, or R₂ and R₃ togetherrepresent —O—CR₂′R₃′—O— wherein R₂′ and R₃′, which may be the same ordifferent, represent a hydrogen atom, C₁₋₆ alkyl, or optionallysubstituted phenyl, or R₂′ and R₃′ together represent oxo or C₂₋₆alkylene, and R₄ represents hydroxyl, optionally substituted C₁₋₆alkylcarbonyloxy, saturated or unsaturated five- or six-memberedheterocyclic oxy, optionally substituted benzoyloxy, C₁₋₃ alkyloxy-C₁₋₃alkyloxy, optionally substituted C₁₋₆ alkylaminocarbonyloxy, optionallysubstituted saturated or unsaturated five- or six-membered heterocycliccarbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy,optionally substituted 1H-indolylcarbonyloxy, saturated or unsaturatedfive- or six-membered heterocyclic thiocarbonyloxy, or oxo in theabsence of a hydrogen atom at the 7-position.

According to another preferred embodiment of the present invention, inthe compound represented by formula (I), Het₁ represents 3-pyridyl, R₁represents hydroxyl, R₂ represents optionally substituted C₁₋₆alkylcarbonyloxy, and R₃ represents optionally substituted C₁₋₆alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, and R₄ represents hydroxyl,optionally substituted C₁₋₆ alkylcarbonyloxy, saturated or unsaturatedfive- or six-membered heterocyclic oxy, optionally substitutedbenzoyloxy, C₁₋₃ alkyloxy-C₁₋₃ alkyloxy, optionally substituted C₁₋₆alkylaminocarbonyloxy, optionally substituted saturated or unsaturatedfive- or six-membered heterocyclic carbonyloxy, optionally substitutedthieno[3,2-b]pyridylcarbonyloxy, optionally substituted1H-indolylcarbonyloxy, saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atomat the 7-position.

According to another preferred embodiment of the present invention, inthe compound represented by formula (I), Het₁ represents 3-pyridyl, R₁represents hydroxyl, R₂ represents optionally substituted C₁₋₆alkylcarbonyloxy, R₃ represents optionally substituted C₁₋₆alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, and R₄ represents hydroxyl,optionally substituted C₁₋₆ alkylcarbonyloxy, optionally substitutedbenzoyloxy, saturated or unsaturated five- or six-membered heterocyclicoxy, optionally substituted saturated or unsaturated five- orsix-membered heterocyclic carbonyloxy, or saturated or unsaturated five-or six-membered heterocyclic thiocarbonyloxy.

According to another preferred embodiment of the present invention, inthe compound represented by formula (I), Het₁ represents 3-pyridyl, R₁represents hydroxyl, and R₂ and R₃ represent optionally substitutedcyclic C₃₋₆ alkylcarbonyloxy.

According to another preferred embodiment of the present invention, inthe compound represented by formula (I),

-   -   Het₁ represents 3-pyridyl,    -   R₁ represents hydroxyl or        -   optionally substituted C₁₋₆ alkylcarbonyloxy or    -   the bond between 5-position and 13-position represents a double        bond in the absence of R₁ and a hydrogen atom at the 5-position,    -   R₂ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy or        -   optionally substituted benzoyloxy,    -   R₃ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy or        -   optionally substituted C₁₋₆ alkylsulfonyloxy, and    -   R₄ represents hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted C₁₋₆ alkylaminocarbonyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic oxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic carbonyloxy,        -   optionally substituted thieno[3,2-b]pyridylcarbonyloxy        -   optionally substituted 1H-indolylcarbonyloxy, or        -   oxo in the absence of a hydrogen atom at the 7-position.

According to another preferred embodiment of the present invention, inthe compound represented by formula (I),

-   -   Het₁ represents 3-pyridyl,    -   R₁ represents hydroxyl or        -   optionally substituted C₁₋₆ alkylcarbonyloxy, or    -   the bond between 5-position and 13-position represents a double        bond in the absence of R1 and a hydrogen atom at the 5-position,    -   R₂ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy,    -   R₃ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy or        -   optionally substituted C₁₋₆ alkylsulfonyloxy, and    -   R₄ represents hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted C₁₋₆ alkylaminocarbonyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic oxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic carbonyloxy, or        -   oxo in the absence of a hydrogen atom at the 7-position.

According to another preferred embodiment of the present invention, inthe compound represented by formula (I),

-   -   Het₁ represents 3-pyridyl,    -   R₁ represents hydroxyl or        -   optionally substituted C₁₋₆ alkylcarbonyloxy, or    -   the bond between 5-position and 13-position represents a double        bond in the absence of R₁ and a hydrogen atom at the 5-position,    -   R₂ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy,    -   R₃ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy,    -   R₄ represents hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic oxy, or        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic carbonyloxy.

According to another preferred embodiment of the present invention, Inthe compound represented by formula (I), Het₁ represents 3-pyridyl, R₁represents hydroxyl, R₂ represents C₁₋₆ alkylcarbonyloxy, and R₃ and/orR₄ represent C₂₋₄ alkylcarbonyloxy.

Further, an agriculturally and horticulturally acceptable salt of thecompound represented by formula (I) include the same as that of thecompound represented by formula (Ib) described below.

A Composition for Use as a Hemipteran Pest Control Agent, Comprising aCompound Represented by Formula (Ia)

According to a preferred embodiment of the present invention, in thecompound represented by formula (Ia), preferably, Het₂ represents3-pyridyl.

Further, according to a preferred embodiment of the present invention,in the compound represented by formula (Ia), R₁₁ represents hydroxyl,C₁₀₆ alkylcarbonyloxy, C₁₋₃ alkyloxy, or benzyloxy, or oxo in theabsence of a hydrogen atom at the 13-position, or the bond between5-position and 13-position represents a double bond in the absence ofR₁₁ and a hydrogen atom at the 5-position. More preferably, R₁₁represents hydroxyl or C₁₋₆ alkylcarbonyloxy, or the bond between5-position and 13-position represents a double bond in the absence ofR₁₁ and a hydrogen atom at the 5-position, still more preferably R₁₁represents hydroxyl.

According to a preferred embodiment of the present invention, in thecompound represented by formula (Ia), R₁₂ represents hydroxyl,optionally substituted C₁₋₁₈ alkylcarbonyloxy, optionally substitutedbenzoyloxy, or C₁₋₃ alkylsulfonyloxy, more preferably optionallysubstituted C₁₋₁₈ alkylcarbonyloxy, still more preferably optionallysubstituted C₁₋₆ alkylcarbonyloxy, still more preferably straight chainor branched chain C₁₋₆ alkylcarbonyloxy (particularly propionyloxy) oroptionally substituted cyclic C₃₋₆ alkylcarbonyloxy.

In a preferred embodiment of the present invention, in the compoundrepresented by formula (Ia), R₁₃ represents a hydrogen atom, hydroxyl,optionally substituted C₁₋₁₈ alkylcarbonyloxy, optionally substitutedbenzoyloxy, C₁₋₆ alkylsulfonyloxy, optionally substitutedbenzenesulfonyloxy, or saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy more preferably optionally substituted C₁₋₆alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, still more preferablyoptionally substituted C₁₋₆ alkylcarbonyloxy, still more preferablystraight chain or branched chain C₂₋₄ alkylcarbonyloxy (particularlypropionyloxy) or optionally substituted cyclic C₃₋₆ alkylcarbonyloxy.

According to a preferred embodiment of the present invention, in thecompound represented by formula (Ia), R₁₂ and R₁₃ together represent—O—CR₁₂′R₁₃′—O—, wherein R₁₂′ and R₁₃′, which may be the same ordifferent, represent a hydrogen atom, C₁₋₆ alkyl, C₁₋₃ alkyloxy, C₂₋₃alkenyl, benzyl, or optionally substituted phenyl, or R₁₂′ and R₁₃′together represent oxo or C₂₋₆ alkylene. More preferably, R₁₂ arid R₁₃together represent —O—CR₁₂′R₁₃′—O—, wherein R₁₂′ and R₁₃′, which may bethe same or different, represent a hydrogen atom, C₁₋₆ alkyl, oroptionally substituted phenyl, or R₁₂′ and R₁₃ ′ together represent oxoor C₂₋₆ alkylene.

According to a preferred embodiment of the present invention, in thecompound represented by formula (Ia), R₁₄ represents a hydrogen atom,hydroxyl, optionally substituted C₁₋₁₈ alkylcarbonyloxy, C₂₋₆alkenylcarbonyloxy, C₂₋₆ alkynyl carbonyloxy, C₁₋₃ alkylsulfonyloxy.benzenesulfonyloxy, benzyloxy, C₁₋₃ alkyloxy, C₁₋₃ alkyloxy-C₁₋₃alkyloxy, C₁₋₃ alkylthio-C₁₋₃ alkyloxy, C₁₋₃ alkyloxy-C₁₋₃ alkyloxy-C₁₋₃alkyloxy, optionally substituted C₁₋₃ alkyloxycarbonyloxy, optionallysubstituted C₁₋₆ alkylaminocarbonyloxy, optionally substitutedbenzoyloxy, saturated or unsaturated five- or six-membered heterocyclicoxy, optionally substituted saturated or unsaturated five- orsix-membered heterocyclic carbonyloxy, optionally substitutedthieno[3,2-b]pyridylcarbonyloxy, optionally substituted1H-indolylcarbonyloxy, or saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atomat the 7-position. More preferably, R₁₄ represents hydroxyl, optionallysubstituted C₁₋₆ alkylcarbonyloxy, optionally substituted benzoyloxy,saturated or unsaturated five- or six-membered heterocyclic oxy, C₁₋₃alkyloxy-C₁₋₃ alkyloxy, optionally substituted C₁₋₆alkylaminocarbonyloxy, optionally substituted saturated or unsaturatedfive- or six-membered heterocyclic carbonyloxy, optionally substitutedthieno[3,2-b]pyridylcarbonyloxy, optionally substituted1H-indolylcarbonyloxy, or saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atomat the 7-position. Still more preferably, R₁₄ represents hydroxyl,optionally substituted C₁₋₆ alkylcarbonyloxy, saturated or unsaturatedfive- or six-membered heterocyclic oxy, optionally substitutedbenzoyloxy, optionally substituted saturated or unsaturated five- orsix-membered heterocyclic carbonyloxy, or saturated or unsaturated five-or six-membered heterocyclic thiocarbonyloxy. Still more preferably, R₁₄represents straight chain or branched chain C₂₋₄ alkylcarbonyloxy(particularly propionyloxy), optionally substituted cyclic C₃₋₆alkylcarbonyloxy, or optionally substituted saturated or unsaturatedfive- or six-membered heterocyclic carbonyloxy.

According to another preferred embodiment of the present invention, inthe compound represented by formula (Ia), Het₂ represents 3-pyridyl, R₁₁represents hydroxyl or C₁₋₆ alkylcarbonyloxy, or the bond between5-position and 13-position represents a double bond in the absence ofR₁₁ and a hydrogen atom at the 5-position, R₁₂ represents optionallysubstituted C₁₋₆ alkylcarbonyloxy, R₁₃ represents optionally substitutedC₁₋₆ alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, or R₁₂ and R₁₃ togetherrepresent —O—CR₁₂′R₁₃′—O— wherein R₁₂′ and R₁₃′, which may be the sameor different, represent a hydrogen atom, C₁₋₆ alkyl, or optionallysubstituted phenyl, or R₁₂′ and R₁₃′ together represent oxo or C₂₋₆alkylene, and R₁₄ represents hydroxyl, optionally substituted C₁₋₆alkylcarbonyloxy, saturated or unsaturated five- or six-memberedheterocyclic oxy, optionally substituted benzoyloxy, C₁₋₃ alkyloxy-C₁₋₃alkyloxy, optionally substituted C₁₋₆ alkylaminocarbonyloxy, optionallysubstituted saturated or unsaturated five- or six-membered heterocycliccarbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy,optionally substituted 1H-indolylcarbonyloxy, saturated or unsaturatedfive- or six-membered heterocyclic thiocarbonyloxy, or oxo in theabsence of a hydrogen atom at the 7-position.

According to another preferred embodiment of the present invention, inthe compound represented by formula (Ia), Het₂ represents 3-pyridyl, R₁₁represents hydroxyl, R₁₂ represents optionally substituted C₁₋₆alkylcarbonyloxy, and R₁₃ represents optionally substituted C₁₋₆alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, and R₁₄ represents hydroxyl,optionally substituted C₁₋₆ alkylcarbonyloxy, saturated or unsaturatedfive- or six-membered heterocyclic oxy, optionally substitutedbenzoyloxy, C₁₋₃ alkyloxy-C₁₋₃ alkyloxy, optionally substituted C₁₋₆alkylaminocarbonyloxy, optionally substituted saturated or unsaturatedfive- or six- membered heterocyclic carbonyloxy, optionally substitutedthieno[3,2-b]pyridylcarbonyloxy, optionally substituted1H-indolylcarbonyloxy, saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atomat the 7-position.

According to another preferred embodiment of the present invention, inthe compound represented by formula (Ia), Het₂ represents 3-pyridyl, R₁₁represents hydroxyl, R₁₂ represents optionally substituted C₁₋₆alkylcarbonyloxy, R₁₃ represents optionally substituted C₁₋₆alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, and R₁₄ represents hydroxyl,optionally substituted C₁₋₆ alkylcarbonyloxy, optionally substitutedbenzoyloxy, saturated or unsaturated five- or six-membered heterocyclicoxy, optionally substituted saturated or unsaturated five- orsix-membered heterocyclic carbonyloxy, or saturated or unsaturated five-or six-membered heterocyclic thiocarbonyloxy.

According to another preferred embodiment of the present invention, inthe compound represented by formula (Ia), Het₂ represents 3-pyridyl, R₁₁represents hydroxyl, and R₁₂ and R₁₃ represent optionally substitutedcyclic C₃₋₆ alkylcarbonyloxy,

According to another preferred embodiment of the present invention, inthe compound represented by formula (Ia),

-   -   Het₂ represents 3-pyridyl,    -   R₁₁ represents hydroxyl or        -   optionally substituted C₁₋₆ alkylcarbonyloxy, or    -   the bond between 5-position and 13-position represents a double        bond in the absence of R₁₁ and a hydrogen atom at the        5-position,    -   R₁₂ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy or        -   optionally substituted benzoyloxy,    -   R₁₃ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy or        -   optionally substituted C₁₋₆ alkylsulfonyloxy, and    -   R₁₄ represents hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy.        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted C₁₋₆ alkylaminocarbonyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic oxy.        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic carbonyloxy,        -   optionally substituted thieno[3,2-b]pyridylcarbonyloxy,        -   optionally substituted 1H-indolylcarbonyloxy, or        -   oxo in the absence of a hydrogen atom at the 7-position,

According to another preferred embodiment of the present invention, inthe compound represented by formula (Ia),

-   -   Het₂ represents 3-pyridyl,    -   R₁₁ represents hydroxyl or        -   optionally substituted C₁₋₆ alkylcarbonyloxy, or    -   the bond between 5-position and 13-position represents a double        bond in the absence of R₁₁ and a hydrogen atom at the        5-position,    -   R₁₂ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy,    -   R₁₃ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy or        -   optionally substituted C₁₋₆ alkylsulfonyloxy, and    -   R₁₄ represents hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted C₂₋₆ alkenylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted C₁₋₆ alkylaminocarbonyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic oxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic carbonyloxy, or        -   oxo in the absence of a hydrogen atom at the 7-position,

According to another preferred embodiment of the present invention, inthe compound represented by formula (Ia), Het₂ represents 3-pyridyl,

-   -   R₁₁ represents hydroxyl or        -   optionally substituted C₁₋₆ alkylcarbonyloxy, or    -   the bond between 5-position and 13-position represents a double        bond in the absence of R₁₁ and a hydrogen atom at the        5-position,    -   R₁₂ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy,    -   R₁₃ represents optionally substituted C₁₋₁₈ alkylcarbonyloxy,    -   R₁₄ represents hydroxyl,        -   optionally substituted C₁₋₁₈ alkylcarbonyloxy,        -   optionally substituted benzoyloxy,        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic oxy, or        -   optionally substituted saturated or unsaturated five- or            six-membered heterocyclic carbonyloxy.

According to another preferred embodiment of the present invention, inthe compound represented by formula (Ia), Het₂ represents 3-pyridyl, R₁₁represents hydroxyl, R₁₂ represents C₁₋₆ alkylcarbonyloxy, and R₁₃and/or R₁₄ represent C₂₋₄ alkylcarbonyloxy,

Further, an agriculturally and horticulturally acceptable salt of thecompound represented by formula (Ia) include the same as that of thecompound represented by formula (Ib) described below.

Compounds of Formula (Ib) or its Agriculturally and HorticulturallyAcceptable Salts

Compounds of formula (Ib) are novel pyripyropene derivatives that arecomprised as a part in the compound represented by formula (I). Inparticular, they have significant insecticidal activity.

According to an embodiment of the present invention, there is providedthe compounds of formula (Ib), excluding a compound wherein Het₁represents 3-pyridyl, R₁ represents hydroxyl, and R₂ and R₃ representpropionyloxy, and R₄ represents hydroxyl.

According to another preferred embodiment of the present invention, inthe compound represented by formula (Ib), R₂ and R₃ represent optionallysubstituted cyclic C₃₋₆ alkylcarbonyloxy, R₄ represents hydroxyl,optionally substituted cyclic C₃₋₆ alkylcarbonyloxy, or optionallysubstituted benzoyloxy. Alternatively, R₂ and R₃ represent propionyloxy,R₄ represents optionally substituted cyclic C₃₋₆ alkylcarbonyloxy, oroptionally substituted saturated or unsaturated five- or six-memberedheterocyclic carbonyloxy.

According to another preferred embodiment of the present invention, inthe compounds represented by formula (Ib), R₂ and R₃ representoptionally substituted cyclic C₃₋₆ alkylcarbonyloxy, R₄ representshydroxyl, optionally substituted cyclic C₃₋₆ alkylcarbonyloxy, oroptionally substituted benzoyloxy.

According to another preferred embodiment of the present invention, inthe compounds represented by formula (Ib), R₂ and R₃ representpropionyloxy, R₄ represents optionally substituted cyclic C₃₋₆alkylcarbonyloxy or optionally substituted saturated or unsaturatedfive- or six-membered heterocyclic carbonyloxy.

According to still another preferred embodiment of the presentinvention, there is provided a pest control agent comprising a compoundrepresented by formula (Ib) or an agriculturally and horticulturallyacceptable salt thereof as an active ingredient.

Agriculturally and horticulturally acceptable salts in the compounds offormula (Ib) include, for example, acid addition salts such ashydrochlorides, nitrates, sulfates, phosphates, or acetates.

Specific examples of the compounds represented by formula (I), (Ia), or(Ib) include compounds shown in Tables 1 to 14 below. In the followingtables, H(═) means that the bond between 5-position and 13-positionrepresents a double bond in the absence of R₁ and a hydrogen atom at the5-position

TABLE 1 Compound No. R₁ R₂ R₃ R₄ Het₁ 1 OH OCOCH₃ OCOCH₃ OCOCH₂CH₃3-pyridyl 2 OH OCOCH₃ OCOCH₃ OCOCH₃CF₂ 3-pyridyl 3 OH OCOCH₃ OCOCH₃OCOCH₂OCH₃ 3-pyridyl 4 OH OCOCH₃ OCOCH₃ OCOCH₂OCOCH₃ 3-pyridyl 5 OHOCOCH₃ OCOCH₃ OCOCH₂CH₂CN 3-pyridyl 6 OH OCOCH₃ OCOCH₃ OCO(CH₂)₂CH₃3-pyridyl 7 OH OCOCH₃ OCOCH₃ OCO(CH₂)₃CH₃ 3-pyridyl 8 OH OCOCH₃ OCOCH₃OCO(CH₂)₄CH₃ 3-pyridyl 9 OH OCOCH₃ OCOCH₃ OCO(CH₂)₅CH₃ 3-pyridyl 10 OHOCOCH₃ OCOCH₃ OCO(CH₂)₆CH₃ 3-pyridyl 11 OH OCOCH₃ OCOCH₃ OCO(CH₂)₁₆CH₃3-pyridyl 12 OH OCOCH₃ OCOCH₃ OCOCH(CH₃)₂ 3-pyridyl 13 OH OCOCH₃ OCOCH₃OCOCH(C₃)₂ 3-pyridyl 14 OH OCOCH₃ OCOCH₃ OCOCH₂CH(CH₃)₂ 3-pyridyl 15 OHOCOCH₃ OCOCH₃ OCO(CH₂)₂CH(CH₃)₂ 3-pyridyl 16 OH OCOCH₃ OCOCH₃ OCO-trans-3-pyridyl CH═CHCH₂CH₃ 17 OH OCOCH₃ OCOCH₃ OCOCH₂C≡OCH₃ 3-pyridyl 18 OHOCOCH₃ OCOCH₃ OCOC≡CCH₂CH₃ 3-pyridyl 19 OH OCOCH₃ OCOCH₃ OCO(CH₃)₂C≡CH3-pyridyl 20 OH OCOCH₃ OCOCH₃ OCO(CH₂)₃CH═CH₂ 3-pyridyl

TABLE 2 Compound No. R₁ R₂ R₃ R₄ Het₁ 21 OH OCOCH₃ OCOCH₃ OCOCH₂C₆H₅3-pyridyl 22 OH OCOCH₃ OCOCH₃ OCO(CH₂)₂C₆H₅ 3-pyridyl 23 OH OCOCH₃OCOCH₃ OCOC₆H₅ 3-pyridyl 24 OH OCOCH₃ OCOCH₃ OCO-(4-Br—C₆H₄) 3-pyridyl25 OH OCOCH₃ OCOCH₃ OCO-(4-N₃—C₆H₄) 3-pyridyl 26 OH OCOCH₃ OCOCH₃OCO-(4-OCF₃—C₆H₄) 3-pyridyl 27 OH OCOCH₃ OCOCH₃ OCO-(4-SO₂CF₃—C₆H₄)3-pyridyl 28 OH OCOCH₃ OCOCH₃ OCO-(3-pyridyl) 3-pyridyl 29 OH OCOCH₃OCOCH₃ OCO-(2-Cl-3-pyridyl) 3-pyridyl 30 OH OCOCH₃ OCOCH₃ OCO-(2-franyl)3-pyridyl 31 OH OCOCH₃ OCOCH₃ OCO-(2-thiazolyl) 3-pyridyl 32 OH OCOCH₃OCOCH₃ OCO-(2-Cl-5-thiazolyl) 3-pyridyl 33 OH OCOCH₃ OCOCH₃OCO-(5-imidazolyl) 3-pyridyl 34 OH OCOCH₃ OCOCH₃ OCS-(1-imidazolyl)3-pyridyl 35 OH OCOCH₃ OCOCH₃ OCOOCH₂C₆H₅ 3-pyridyl 36 OH OCOCH₃ OCOCH₃OSO₂CH₃ 3-pyridyl 37 OH OCOCH₃ OCOCH₃ OSO₂C₆H₅ 3-pyridyl 38 OH OCOCH₃OCOCH₃ OCONHCH₂CH₃ 3-pyridyl 39 OH OCOCH₃ OCOCH₃ OCONH(CH₂)CH₃ 3-pyridyl40 OH OCOCH₃ OCOCH₃ OCONHCH₂C₆H₅ 3-pyridyl

TABLE 3 Compound No. R₁ R₂ R₃ R₄ Het₁ 41 OH OCOCH₃ OCOCH₃ OCH₂C₆H₅3-pyridyl 42 OH OCOCH₃ OCOCH₃ OCH₂SCH₃ 3-pyridyl 43 OH OCOCH₃ OCOCH₃OCH₂OCH₃ 3-pyridyl 44 OH OCOCH₃ OCOCH₃ OCH₂OCH₂CH₂OCH₃ 3-pyridyl 45 OHOCOCH₃ OCOCH₃ O-(2-tetrahydropyranyl) 3-pyridyl 46 OH OCOCH₃ OCOCH₃O-(tetra-O-benzyl-mannosyl) 3-pyridyl 47 OH OCOCH₃ OCOCH₃ H 3-pyridyl 48OH OCOCH₃ OCOCH₃ OCO—c-C₃H₅ 3-pyridyl 49 OH OCOCH₃ OCOCH₃ OH 3-pyridyl50 OH OCOCH₃ OCOCH₃ ═O 3-pyridyl 51 OH OCOCH₃ OCOCH2CH3 OCOCH₃ 3-pyridyl52 OH OCOCH₃ OCOCH2CH3 OCOCH₂CH₃ 3-pyridyl 53 OH OCOCH₃ OCOCH₂CH₃ H3-pyridyl 54 OH OCOCH₃ OCO(CH₂)₂CH₃ OCOCH₃ 3-pyridyl 55 OH OCOCH₃OCO(CH₂)₂CH₃ OH 3-pyridyl 56 OH OCOCH₃ OCO(CH₂)₃CH₃ OCOCH₃ 3-pyridyl 57OH OCOCH₃ OCOCH(CH)₃)₂ OCOCH₃ 3-pyridyl 58 OH OCOCH₃ OCOC₆H₅ OCOCH₃3-pyridyl 59 OH OCOCH₃ OCOC₆H₅ OH 3-pyridyl 60 OH OCOCH₃OCS-(1-imidazolyl) OCOCH₃ 3-pyridyl

TABLE 4 Compound No. R₁ R₂ R₃ R₄ Het₁ 61 OH OCOCH₃ OSO₂CH₃ OCOCH₃3-pyridyl 62 OH OCOCH₃ OSO₂CH₃ OCO(CH₂)₃CH₃ 3-pyridyl 63 OH OCOCH₃OSO₂C₆H₅ OCOCH₃ 3-pyridyl 64 OH OCOCH₃ OSO₂CH₂CH₃ OCOCH₃ 3-pyridyl 65 OHOCOCH₃ OSO₂CH₂CH₂CH₃ OCOCH₃ 3-pyridyl 66 OH OCOCH₃ OSO₂CH₂CH₃ OH3-pyridyl 67 OH OCOCH₃ OSO₂CH₂CH₂CH₃ OH 3-pyridyl 68 OH OCOCH₃ OH OH3-pyridyl 69 OH OCOCH₃ OH OCOCH₃ 3-pyridyl 70 OH OCOCH₃ H H 3-pyridyl 71OH OCOCH₃ H OCOCH₂CH₃ 3-pyridyl 72 OH OCOCH₂CH₃ OCOCH₃ OCOCH₃ 3-pyridyl73 OH OCOCH₂CH₃ OCOCH₂CH₃ OH 3-pyridyl 74 OH OCOCH₂CH₃ OCOCH₂CH₃ OCOCH₃3-pyridyl 75 OH OCOCH₂CH₃ OCOCH₃ OCOCH₂CH₃ 3-pyridyl 76 OH OCOCH₂CH₃OCOCH₂CH₃ OCOCH₂CH₃ 3-pyridyl 77 OH OCOCH₂CH₃ OCOCH₂CH₃ OCOC₆H₅3-pyridyl 78 OH OCOCH₂CH₃ OCOCH₂CH₃ H 3-pyridyl 79 OH OCOCH₂CH₃ H H3-pyridyl 80 OH OCO(CH₂)₂CH₃ OCOCH₃ OCOCH₃ 3-pyridyl

TABLE 5 Compound No. R₁ R₂ R₃ R₄ Het₁ 81 OH OCO(CH₂)₂CH₃ OCO(CH₂)₂CH₃ OH3-pyridyl 82 OH OCO(CH₂)₂CH₃ OCO(CH₂)₂CH₃ OCO(CH₂)₂CH₃ 3-pyridyl 83 OHOCO(CH₂)₂CH₃ OCO(CH₂)₂CH₃ OCOCH₃ 3-pyridyl 84 OH OCO(CH₂)₃CH₃ OCOCH₃OCOCH₃ 3-pyridyl 85 OH OCO(CH₂)₃CH₃ OCO(CH₂)₃CH₃ OCO(CH₂)₃CH₃ 3-pyridyl86 OH OCO(CH₂)₃CH₃ OSO₂CH₃ OCO(CH₂)₃CH₃ 3-pyridyl 87 OH OCO(CH₂)₃CH₃OSO₂CH₃ OH 3-pyridyl 88 OH OCO(CH₂)₁₆CH₃ OCO(CH₂)₁₆CH₃ OCO(CH₂)₁₆CH₃3-pyridyl 89 OH OCOCH(CH₃)₂ OCOCH₃ OCOCH₃ 3-pyridyl 90 OH OCOCH(CH₃)₂OCOCH(CH₃)₂ OCOCH(CH₃)₂ 3-pyridyl 91 OH OCOC(CH₃)₃ OCOC(CH₃)₃ OCOC(CH₃)₃3-pyridyl 92 OH OCOC₆H₅ OCOCH₃ OCOCH₃ 3-pyridyl 93 OH OCOC₆H₅ OSO₂CH₃ OH3-pyridyl 94 OH OCOC₆H₅ OSO₂CH₃ OCOCH₃ 3-pyridyl 95 OH OCOC₆H₅ OSO₂CH₃OCO(CH₂)₃CH₃ 3-pyridyl 96 OH OCO-(4-Br—C₆H₄) OCO-(4-Br—C₆H₄)OCO-(4-Br—C₆H₄) 3-pyridyl 97 OH OCO-(4-N₃—C₆H₄) OSO₂CH₃ OCOCH₃ 3-pyridyl98 OH OSO₂CH₃ OSO₂CH₃ OH 3-pyridyl 99 OH OSO₂CH₃ OSO₂CH₃ OSO₂CH₃3-pyridyl 100 OH OSO₂CH₃ OSO₂CH₃ OCOCH₃ 3-pyridyl

TABLE 6 Compound No. R₁ R₂ R₃ R₄ Het₁ 101 OH OSO₂CH₃ OH OH 3-pyridyl 102OH OH OH OH 3-pyridyl 103 OH OH OH OCOCH₃ 3-pyridyl 104 OH OH OHOCO(CH₂)₃CH₃ 3-pyridyl 105 OH OH OH OCH₂OCH₂CH₂OCH₃ 3-pyridyl 106 OH OHOCOCH₃ OH 3-pyridyl 107 OH OH OCOCH₂CH₃ OH 3-pyridyl 108 OH OHOCO(CH₂)₂CH₃ OH 3-pyridyl 109 OH OH OCO(CH₂)₃CH₃ OH 3-pyridyl 110 OH OHOCOCH(CH₃)₂ OH 3-pyridyl 111 OH OH OSO₂CH₃ OH 3-pyridyl 112 OH OHOSO₂CH₂CH₃ OH 3-pyridyl 113 OH OH OSO₂CH₂CH₂CH₃ OH 3-pyridyl 114 OH OHOSO₂CH(CH₃)₂ OH 3-pyridyl 115 OH OH OSO₂C₆H₅ OH 3-pyridyl 116 OH OHOSO₂-(4-CH₃—C₆H₄) OH 3-pyridyl 117 OH OH OCO-(4-Br—C₆H₄) OH 3-pyridyl118 OH OH OCO(CH₂)₃CH₃ OCO(CH₂)₃CH₃ 3-pyridyl 119 OH OH OSO₂CH₃ OSO₂CH₃3-pyridyl 120 OH OH OSO₂CH₃ OCOCH₃ 3-pyridyl

TABLE 7 Compound No. R₁ R₂ R₃ R₄ Het₁ 121 OH OH OSO₂CH₃ OCOCH₃ 3-pyridyl122 OH OH OSO₂CH₃ OCO(CH₂)₃CH₃ 3-pyridyl 123 OH OH OSO₂C₆H₅ OCOCH₃3-pyridyl 124 OH OH OSO₂C₆H₅ OSO₂C₆H₅ 3-pyridyl 125 OH —O—CH(CH₃)—O—OCO(CH₂)₃CH₃ 3-pyridyl 126 OH —O—CH(C₂H₅)—O— OH 3-pyridyl 127 OH—O—CH(C₂H₅)—O— OCO(CH₂)₃CH₃ 3-pyridyl 128 OH —O—CH(CH═CH₂)—O— OH3-pyridyl 129 OH —O—CH(CH═CH₂)—O— OCO(CH₂)₃CH₃ 3-pyridyl 130 OH—O—CH(CH(CH₃)₂)—O— OH 3-pyridyl 131 OH —O—CH(CH(CH₃)₂)—O— OCO(CH₂)₃CH₃3-pyridyl 132 OH —O—CH(OCH₃)—O— OH 3-pyridyl 133 OH —O—CH(C(CH₃)₃)—O—OCO(CH₂)₃CH₃ 3-pyridyl 134 OH —O—CH(CH₂C₆H₅)—O— OH 3-pyridyl 135 OH—O—C(CH₃)₂—O— OH 3-pyridyl 136 OH —O—C(CH₃)₂—O— OCOCH₃ 3-pyridyl 137 OH—O—C(CH₃)₂—O— OCO(CH₂)₃CH₃ 3-pyridyl 138 OH —O—C(CH₃C₆H₅)—O— OH3-pyridyl 139 OH —O—C(CH₃)(C₆H₅)—O— OCO(CH₂)₃CH₃ 3-pyridyl 140 OH—O—CH(C₆H₅)—O— OH 3-pyridyl

TABLE 8 Compound No. R₁ R₂ R₃ R₄ Het₁ 141 OH —O—CH(C₆H₅)—O— OCOCH₃3-pyridyl 142 OH —O—CH(OCH₃)—O— OCO(CH₂)₃CH₃ 3-pyridyl 143 OH—O—CH(C₆H₅)—O— OCO(CH₂)₃CH₃ 3-pyridyl 144 OH —O—CH(3-CH₃—C₆H₄)—O— OH3-pyridyl 145 OH —O—CH(3-CH₃—C₆H₄)—O— OCO(CH₂)₃CH₃ 3-pyridyl 146 OH—O—CH(2-CH₃—C₆H₄)—O— OH 3-pyridyl 147 OH —O—CH(4-CH₃—C₆H₄)—O—OCO(CH₂)₃CH₃ 3-pyridyl 148 OH —O—CH(3-F—C₆H₄)—O— OH 3-pyridyl 149 OH—O—CH(2-F—C₆H₄)—O— OCO(CH₂)₃CH₃ 3-pyridyl 150 OH —O—CH(4-F—C₆H₄)—O—OCO(CH₂)₃CH₃ 3-pyridyl 151 OH —O—CH(4-NO₂—C₆H₄)—O— OH 3-pyridyl 152 OH—O—CH(4-NO₂—C₆H₄)—O— OCO(CH₂)₃CH₃ 3-pyridyl 153 OH —O—CH(4-OCH₃—C₆H₄)—O—OH 3-pyridyl 154 OH —O—CH(4-OCH₃—C₆H₄)—O— OCO(CH₂)₃CH₃ 3-pyridyl 155 OH—O—C(spiro-c-C₅H₈)—O— OH 3-pyridyl 156 OH —O—C(spiro-c-C₅H₈)—O—OCO(CH₂)₃CH₃ 3-pyridyl 157 OH —O—C(spiro-c-C₆H₁₀)—O— OH 3-pyridyl 158 OH—O—C(spiro-c-C₆H₁₀)—O— OCO(CH₂)₃CH₃ 3-pyridyl 159 OH —O—CO—O— OH3-pyridyl 160 OH —O—CO—O— OCO-1-imidazolyl 3-pyridyl

TABLE 9 Compound No. R₁ R₂ R₃ R₄ Het₁ 161 OH —O—CO—O— OCO(CH₂)₃CH₃3-pyridyl 162 OCOCH₃ OCOCH₃ OCOCH₃ OCOCH₃ 3-pyridyl 163 OCOCH₃ OCOCH₃OCOCH₃ OH 3-pyridyl 164 OCOCH₃ OCOCH₃ OCO(CH₂)₂CH₃ OCOCH₃ 3-pyridyl 165OCOCH₃ OH OH OCOCH₃ 3-pyridyl 166 OCOCH₃ OCOCH₂CH₃ OCOCH₂CH₃ OCOCH₂CH₃3-pyridyl 167 OCOCH₂CH₃ OCOCH₂CH₃ OCOCH₂CH₃ OCOCH₂CH₃ 3-pyridyl 168OCOCH₂CH₃ OCOCH₃ OCOCH₃ OCOCH₃ 3-pyridyl 169 OCO(CH₂)₃CH₃ OCOCH₃ OCOCH₃OCOCH₃ 3-pyridyl 170 OCO(CH₂)₃CH₃ OCOCH₃ OCOCH₃ OCO(CH₂)₃CH₃ 3-pyridyl171 OCO(CH₂)₂CH₃ OCOCH₃ OCOCH₃ OCOCH₃ 3-pyridyl 172 OCH₃ OCOCH₃ OCOCH₃OCOCH₃ 3-pyridyl 173 H(═) OSO₂CH₃ OSO₂CH₃ OH 3-pyridyl 174 H(═) OCOC₆H₅OSO₂CH₃ OCOCH₃ 3-pyridyl 175 H(═) OH OH OCOCH₃ 3-pyridyl 176 H(═) OCOCH₃OCOCH₃ ═O 3-pyridyl 177 H(═) —O—CH(C₆H₅)—O— OCOCH₃ 3-pyridyl 178 H(═)—O—CH(CH(CH₃)₂)—O— OH 3-pyridyl 179 H(═) —O—CH(4-NO₂—C₆H₄)—O— OH3-pyridyl 180 H(═) OCOCH₃ OCOCH₃ OCOCH₃ 3-pyridyl

TABLE 10 Compound No. R₁ R₂ R₃ R₄ Het₁ 181 H(═) OH OH OH 3-pyridyl 182H(═) OCOCH₃ OCOCH₃ OH 3-pyridyl 183 H(═) OCOCH₃ OCOCH₃ OCH₂SCH₃3-pyridyl 184 H(═) OCOCH₃ OCOCH₃ OCH₂OCH₃ 3-pyridyl 185 H(═) OCOCH₃OCOCH₃ OCO(CH₂)₃CH₃ 3-pyridyl 186 H(═) OCOCH₃ OCOCH₃ OCO(CH₂)₂Ph3-pyridyl 187 H(═) OCOCH₃ OSO₂CH₃ OCOCH₃ 3-pyridyl 188 H(═) OCOCH₂CH₃OCOCH₂CH₃ OCOCH₂CH₃ 3-pyridyl 189 H(═) OCOCH₂CH₃ OCOCH₂CH₃ OH 3-pyridyl190 H(═) OH OSO₂CH₃ OH 3-pyridyl 191 H(═) OH OH OCO(CH₂)₃CH₃ 3-pyridyl192 H(═) —O—C(CH₃)₂—O— OH 3-pyridyl 193 H(═) —O—C(CH₃)₂—O— OCO(CH₂)₃CH₃3-pyridyl 194 H(═) —O—CH(C₆H₅)—O— OH 3-pyridyl 195 H(═) —O—CH(C₆H₅)—O—OCO(CH₂)₃CH₃ 3-pyridyl 196 H(═) —O—CH(4-OCH₃—C₆H₄)—O— OH 3-pyridyl 197H(═) —O—CH(C₂H₅)—O— OH 3-pyridyl 198 H(═) —O—CH(C(CH₃)₂)—O— OH 3-pyridyl199 H(═) —O—CH(CH₂C₆H₅)—O— OH 3-pyridyl 200 ═O OH OH OH 3-pyridyl

TABLE 11 Compound No. R₁ R₂ R₃ R₄ Het₁ 201 ═O OCOCH₃ OCOCH₃ ═O 3-pyridyl202 ═O OCOCH₃ OCOCH₃ OH 3-pyridyl 203 ═O OCOCH₃ OCOCH₃ OCOCH₃ 3-pyridyl204 ═O OCOCH₂CH₃ OCOCH₂CH₃ OCOCH₂CH₃ 3-pyridyl 205 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(3-Pyridyl) 3-pyridyl 206 OH OCOCH₂CH₃ OCOCH₂CH₃OCOCH(CH₃)₂ 3-pyridyl 207 OH OCOCH₂CH₃ OCOCH₂CH₃ OCOC(CH₃)₃ 3-pyridyl208 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(4-CF₃—C₆H₄) 3-pyridyl 209 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(1-imidazolyl) 3-pyridyl 210 OH OCOCH₂CH₃ OCOCH₂CH₃OCONH(CH₂)₂CH₃ 3-pyridyl 211 OH OCOCH₂CH₃ OCOCH₂CH₃O-(2-tetrahydropyranyl) 3-pyridyl 212 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(6-Cl-3-pyridyl) 3-pyridyl 213 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO—c-C₃H₅3-pyridyl 214 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO—c-C₄H₇ 3-pyridyl 215 OHOCOCH₂CH₃ OCOCH₂CH₃ OCOCH═CH 3-pyridyl 216 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(4-pyridyl) 3-pyridyl 217 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(2-pyridyl)3-pyridyl 218 OH OCO—c-C₃H₅ OCO—c-C₃H₅ OCO—c-C₃H₅ 3-pyridyl 219 OHOCO—c-C₄H₇ OCO—c-C₄H₇ OCO—c-C₄H₇ 3-pyridyl 220 OH OCOC₆H₅ OCOC₆H₅OCOC₆H₅ 3-pyridyl

TABLE 12 Compound No. R₁ R₂ R₃ R₄ Het₁ 221 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(6-CF₃-3-pyridyl) 3-pyridyl 222 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(4-CF₃-3-pyridyl) 3-pyridyl 223 OH OCOCH₂CH₃ OCOCH₂CF₃ OCOCH₂CF₃3-pyridyl 224 OH OCOCH₂CH₃ OCOCH₂CH₃ OCOCH₂CF₃ 3-pyridyl 225 OHOCOCH₂CH₃ OCOCH₂CH₃ OCOCH₂CH₃ 3-pyridyl 226 OH OCOCH₂CH₃ OCOCH₂CH₃OCOCH₂CH₃ 3-pyridyl 227 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(3-F-4-pyridyl)3-pyridyl 228 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(3-Cl-4-pyridyl) 3-pyridyl 229OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(3-CH₃-2-pyridyl) 3-pyridyl 230 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(3-COC₆H₅-2-pyridyl) 3-pyridyl 231 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(3-OCH₂CH₂CH₃-2-pyridyl) 3-pyridyl 232 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(6-F-3-pyridyl) 3-pyridyl 233 OH OCO—c-C₅H₉ OCO—c-C₅H₉ OCO—c-C₅H₉3-pyridyl 234 OH OCO—c-C₆H₁₁ OCO—c-C₆H₁₁ OCO—c-C₆H₁₁ 3-pyridyl 235 OHOCOCH₂CN OCOCH₂CN OCOCH₂CN 3-pyridyl 236 OCOCH₂—c-C₃H₅ OCOCH₂—c-C₃H₅OCOCH₂—c-C₃H₅ OCOCH₂—c-C₃H₅ 3-pyridyl 237 OH OCOCH₂—c-C₃H₅ OCOCH₂—c-C₃H₅OCOCH₂—c-C₃H₅ 3-pyridyl 238 OH OCO-(1-CH₃-2,2-diF—c-C₃H₂)OCO-(1-CH₃-2,2-diF—c-C₃H₂) OCO-(1-CH₃-2,2-diF—c-C₃H₂) 3-pyridyl 239 OHOCOCH₂CH₃ OCOCH₂CH₃ OCO-(4-CH₃-3-pyridyl) 3-pyridyl 240 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(4-Cl-3-pyridyl) 3-pyridyl

TABLE 13 Compound No. R₁ R₂ R₃ R₄ Het₁ 241 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(4-COOCH₃-3-pyridyl) 3-pyridyl 242 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-[5-(CF₃)-thieno[3,2-b]pyridin-6-yl] 3-pyridyl 243 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(2-CN—C₆H₄) 3-pyridyl 244 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(2-CF₃—C₆H₄) 3-pyridyl 245 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(2-F—C₆H₄)3-pyridyl 246 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(2-NO₂—C₆H₄) 3-pyridyl 247 OHOCOCH₂CH₃ OCOCH₂CH₃ OCO-(2-Cl-3-pyridyl) 3-pyridyl 248 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(2-Cl-6-CH₃-3-pyridyl) 3-pyridyl 249 OH OCOCH₂CH₃OCOCH₂CH₃ OCH₂OCH₃ 3-pyridyl 250 OH OCO-(2,2-diF—c-C₃H₃)OCO-(2,2-diF—c-C₃H₃) OCO-(2,2-diF—c-C₃H₃) 3-pyridyl 251 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(3-SC(CH₃)₃-2-pyridyl) 3-pyridyl 252 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(3,5-diF-2-pyridyl) 3-pyridyl 253 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-2-pyrazinyl 3-pyridyl 254 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-4-thiazolyl3-pyridyl 255 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(3-Cl-2-thienyl) 3-pyridyl 256OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(6-CH₃-3-pyridyl) 3-pyridyl 257 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(6-Cl-2-pyridyl) 3-pyridyl 258 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(6-F-2-pyridyl) 3-pyridyl 259 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(1-CH₃—1H-indolyl) 3-pyridyl 260 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(3-Cl-2-pyridyl) 3-pyridyl

TABLE 14 Compound No. R₁ R₂ R₃ R₄ Het₁ 261 OH OCO-c-C₃H₅ OCO-c-C₃H₅ OH3-pyridyl 262 OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(2-F-3-pyridyl) 3-pyridyl 263OH OCOCH₂CH₃ OCOCH₂CH₃ OCO-(4-CN—C₆H₄) 3-pyridyl 264 OH OCOCH₂CH₃OCOCH₂CH₃ OCO-(3-CN—C₆H₄) 3-pyridyl 265 OH OCOCH₂CH₃ OCOCH₂CH₃OCO-(3-CF₃—C₆H₄) 3-pyridyl 266 OH OCOCH₂CH₃ OCOCH₂CH₃ OCOCH₂(2-pyridyl)3-pyridyl 267 OH OCOCH₂CH₃ OCOCH₂CH₃ OCOCH₂(3-pyridyl) 3-pyridyl 268 OHOCOCH₂CH₃ OCOCH₂CH₃ OCOCH₂S(4-pyridyl) 3-pyridyl 269 OH OCO-c-C₃H₅OCO-c-C₃H₅ OCO-(2-CN—C₆H₄) 3-pyridyl 270 OH OCO-c-C₃H₅ OCO-c-C₃H₅OCO-(4-CF₃-3-pyridyl) 3-pyridyl 271 OH OCO-c-C₃H₅ OCO-c-C₃H₅OCO-(3-Cl-2-pyridyl) 3-pyridyl 272 OH —O—CH(C₆H₅)—O— ═O 3-pyridyl 273 OH—O—CH(4-OCH₃—C₆H₄)—O— ═O 3-pyridyl 274 OCO(CH₂)₃CH₃ —O—CO—O—OCO(CH₂)₃CH3 3-pyridyl 275 OCOCH₃ —O—CH(C₆H₅)—O— OCOCH₃ 3-pyridyl 276 ═O—O—CH(4-OCH₃—C₆H₄)—O— OH 3-pyridyl

Production Process

The composition according to the present invention can be prepared bymixing the compound represented by formula (I), (Ia), or (Ib) as activeingredient with an agriculturally and horticulturally acceptablecarrier. The compound represented by formula (I), (Ia), or (Ib)according to the present invention can be produced according to thefollowing procedure.

Among the compounds according to the present invention, the compoundsrepresented by formula (II) can be synthesized by the method describedin Japanese Patent Laid-Open Publication No. 259569/1996, JapanesePatent Laid-Open Publication No. 269062/1996, Japanese Patent Laid-OpenPublication No. 269065/1996, or Journal of Antibiotics (1997), 50(3),pp. 229-36. When pyripyropene A is used as a starting material,pyripyropene A, produced by the method described in Journal of Societyof Synthetic Organic Chemistry, Japan (1998), Vol. 56, No. 6, pp.478-488 or WO 94/09417, may be used as the starting material.

wherein

-   -   R₁ represents hydroxyl, optionally substituted C₁₋₆        alkylcarbonyloxy, optionally substituted C₂₋₆        alkenylcarbonyloxy, optionally substituted C₂₋₆ alkynyl        carbonyloxy, optionally substituted C₁₋₆ alkyloxy, optionally        substituted C₂₋₆ alkenyloxy, optionally substituted C₂₋₆        alkynyloxy, optionally substituted benzyloxy, or oxo in the        absence of a hydrogen atom at the 13-position, and    -   R₂, R₃ and R₄ are as defined in formula (I).

Further, among the compounds according to the present invention, thecompounds represented by formula (III) can be synthesized by the methoddescribed in Japanese Patent Laid-Open Publication No. 269063/1996,Japanese Patent Laid-Open Publication No. 269066/1996.

-   -   wherein R₂, R₃ and R₄ are as defined in formula (I).

Use

Insect species against which pyripyropene derivatives of formula (I) or(Ib) according to the present invention have control effect include:Iepidopteran pests, for example, Spodoptera litura, Mamestra brassicae,Pseudaletia separata, green caterpillar, Plutella xylostella, Spodopteraexigua, Chilo suppressalis, Cnaphalocrocis medinalis, Tortricidae,Carposinidae, Lyonetildae, Lymantriidae, pests belonging to the genusAgrotis spp., pests belonging to the genus Helicoverpa spp., and pestsbelonging to the genus Heliothis spp.; hemipteran pests, for example,Aphidoidea including Aphididae, Adelgidae and Phylloxeridae such asMyzus persicae, Aphis gossypii, Aphis fabae, Aphis maidis (corn-leafaphid), Acyrthosiphon pisum, Aulacorthum solani, Aphis craccivora,Macrosiphum euphorbiae, Macrosiphum avenae, Metopolophium dirhodum,Rhopalosiphum padi, Schizaphis graminum, Brevicoryne brassicae, Lipaphiserysimi, Aphis citricola, Rosy apple aphid, Eriosorna lanigerum,Toxoptera aurantii, and Toxoptera citricidus; Deitocephalidae such asNephotettix cincticeps, Delphacidae such as Laodelphax striatellus,Nilaparvata lugens, and Sogatella furcifera; Pentatomidae such asEysarcoris ventralis, Nezara viridula, and Trigonotylus coelestiafium;Aleyrodidae such as Bemisia argentifolii, Bemisia tabaci, andTrialieurodes vaporariorum; Diaspididae, Margarodidae, Ortheziidae,Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae,Eriococcidae, Asterolecaniidae, Beesonidae, Lecanodiaspididae, orCerococcidae, such as Pseudococcus comstocki and Planococcus citriRisso; Coleoptera pests, for example, Lissorhoptrus oryzophilus,Caflosobruchuys chienensis, Tenebrio molitor, Diabrotica virgiferavirgifera, Diabrotica undecimpunctata howardi, Anomala cuprea, Anomalarufocuprea, Phyllotreta striolata, Aulacophora femoralis, Leptinotarsadecemlineata, Oulema oryzae, Carposinidae, and Cerambycidae; Acari, forexample, Tetranychus urticae, Tetranychus kanzawai, and Panonychuscitri; Hymenopteran pests, for example, Tenthredinidae; Orthopteranpests, for example, Acrididae; Dipteran pests, for example, Museidae andAgromyzidae; Thysanopteran pests, for example, Thrips palmi andFrankliniella occidentalis; Plant Parasitic Nematodes, for example,Meloidogyne hapla, Pratylenchus spp., Aphelenchoides besseyi andBursaphelenchus xylophilus; and parasites of animals, for example,Siphonaptera, Anoplura, mites such as Boophilus microplus, Haemaphysalislongicornis, Rhipicephalus sanguineus, and Scarcoptes scabiei. Preferredare hemipteran pests.

The compound represented by formula (Ia) accordingly to the presentinvention has significant control effect against hemipteran pests.Preferred hemipteran pests are selected from Aphidoidea such asAphididae, Adelgidae, and Phylloxeridae, particularly preferablyAphididae; Coccoidea such as Diaspididae, Margarodidae, Ortheziidae,Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae,Eriococcidae, Asterolecaniidae. Beesonidae, Lecanodiaspididae, andCerococcidae; and Aleyrodidae. More preferred are Myzus persicae, Aphisgossypii, Aphis fabae, Aphis maidis (corn-leaf aphid), Acyrthosiphonpisum, Aulacorthum solani, Aphis craccivora, Macrosiphum euphorbiae,Macrosiphum avenae, Metopolophium dirhodum, Rhopafosiphum padi,Schizaphis graminum, Brevicoryne brassicae, Lipaphis erysimi, Aphiscitricoia, Rosy apple aphid, Eriosoma lanigerum, Toxoptera aurantii,Toxoptera citricidus, and Pseudoeoccus comstocki.

The composition according to the present invention can be prescribed inany suitable formulation, such as emulsifiable concentrates, liquidformulations, suspension, wettable powder, flowables, dust, granules,tablets, oil solutions, aerosols, or smoking agents by using suitableagriculturally and horticulturally acceptable carriers. Accordingly, thecarrier include solid carriers, liquid carriers, gaseous carriers,surfactants, dispersants and/or other adjuvants for formulations, andthe like.

Solid carriers usable herein include, for example, talc, bentonite,clay, kaolin, diatomaceous earth, vermiculite, white carbon, and calciumcarbonate.

Examples of liquid carriers include: alcohols, such as methanol,n-hexanol, and ethylene glycol; ketones, such as acetone, methyl ethylketone, and cyclohexanone; aliphatic hydrocarbons, such as n-hexane,kerosine, and kerosene; aromatic hydrocarbons, such as toluene, xylene,and methylnaphthalene; ethers, such as diethyl ether, dioxane, andtetrahydrofuran; esters, such as ethyl acetate; nitriles, such asacetonitrile and isobutyronitrile; acid amides, such asdimethylformamide and dimethylacetamide; vegetable oils, such as soybean oil and cotton seed oil; dimethylsulfoxide; and water.

Gaseous carriers include, for example, LPG, air, nitrogen, carbondioxide, and dimethyl ether.

Surfactants or dispersants usable, for example, for emulsifying,dispersing, or spreading include, for example, alkylsulfonic esters,alkyl(aryl)sulfonic acid salts, polyoxyalkylene alkyl(aryl) ethers,polyhydric alcohol esters, and lignin sulfonic acid salts.

Adjuvants usable for improving the properties of formulations include,for example, carboxymethylcellulose, gum arabic, polyethylene glycol,and calcium stearate.

The above carriers, surfactants, dispersants, and adjuvant may be usedeither solely or in combination according to need.

The content of the active ingredient in the formulation is notparticularly limited. In general, however, the content of the activeingredient is 1 to 75% by weight for emulsifiable concentrates, 0.3 to25% by weight for dust, 1 to 90% by weight for wettable powder, and 0.5to 10% by weight for granules.

The compound represented by formula (I), (Ia), (Ib), or anagriculturally and horticulturally acceptable salt thereof and the aboveformulations comprising the same may be applied as such or afterdilution to plants or soil. Therefore, according to another aspect ofthe present invention, there is provided a method for controlling apest, comprising applying an effective amount of a compound representedby formula (I) or an agriculturally and horticulturally acceptable saltthereof to a plant or soil. According to still another aspect of thepresent invention, there is provided a method for controlling ahemipteran pest, comprising applying an effective amount of a compoundrepresented by formula (Ia) or an agriculturally and horticulturallyacceptable salt thereof to a plant or soil. According to a furtheraspect of the present invention, there is provided a method forcontrolling a pest, comprising applying an effective amount of acompound represented by formula (Ib) or an agriculturally andhorticulturally acceptable salt thereof to a plant or soil. Preferredmethods usable for applying the compound or formulation to plants orsoil include spreading treatment, soil treatment, surface treatment, andfumigation treatment.

Spreading treatments include, for example, spreading, spraying, misting,atomizing, granule application, and submerged application. Soiltreatments include, for example, soil affusion and soil mixing. Examplesof surface treatments include, for example, coating, dust coating, andcovering. Fumigation treatments include, for example, covering of soilwith a polyethylene film after soil injection. Accordingly, the controlmethod according to the present invention comprises a method in whichthe compound represented by formula (I), (Ia), or (Ib) or a formulationcomprising the same is applied by fumigation in a sealed space.

The composition according to the present invention may be used as amixture or in a combination with, for example, other insecticides,fungicides, miticides, herbicides, plant growth-regulating agents, orfertilizers. Agents which may be mixed or used in combination includethose described, for example, in The Pesticide Manual, 13th edition,published by The British Crop Protection Council; and SHIBUYA INDEX, the10th edition, 2005, published by SHIBUYA INDEX RESEARCH GROUP. Morespecifically, insecticides usable herein include, for example,organophosphate ester compounds such as acephate, dichlorvos, EPN,fenitrothion, fenamifos, prothiofos, profenofos, pyraclofos,chlorpyrifos-methyl, and diazinon; carbamate compounds such as methomyl,thiodicarb, aidicarb, oxamyl, propoxur, carbaryl, fenobucarb,ethiofencarb, fenothiocarb, pirmicarb, carbofuran, and benfuracarb;nereistoxin derivatives such as cartap and thiocyclam; organochlorinecompounds such as dicofol and tetradifon; pyrethroid compounds such aspermethrin, tefluthrin, cypermethrin, deltamethrin, cyhalothrin,fenvalerate, fluvalinate, ethofenprox, and silafluofen; benzoyl ureacompounds such as diflubenzuron, teflubenzuron, flufenoxuron, andchlorfluazuron; juvenile hormone-like compounds such as methoprene; andmolting hormone-like compounds such as chromafenozide. Other compoundsusable herein include buprofezin, hexythiazox, amitraz, chlordimeform,pyridaben, fenpyroxymate, pyrimidifen, tebufenpyrad, fluacrypyrim,acequinocyl, cyflumetofen, flubendiamide, ethiprole, fipronil,ethoxazole, imidacloprid, chlothianrdin, pymetrozine, bifenazate,spirodiclofen, spiromesifen, flonicamid, chlorfenapyr, pyriproxyfene,indoxacarb, pyridalyl, or spinosad, avermectin, milbemycin,organometallic compounds, dinitro compounds, organosulfur compounds,urea compounds, triazine compounds, hydrazine compounds.

The composition according to the present invention may also be used as amixture or in a combination with microbial pesticides such as BTformulations and entomopathogenic viral agents.

Fungicides usable herein include, for example, strobilurin compoundssuch as azoxystrobin, kresoxym-methyl, and trifloxystrobin;anilinopyrimidine compounds such as mepanipyrim, pyrimethanil, andcyprodinil; azole compounds such as triadimefon, bitertanol,triflumizole, etaconazole, propiconazole, penconazole, flusilazole,myclobutanil, cyproconazole, tebuconazole, hexaconazole, prochloraz, andsimeconazole; quinoxaline compounds such as quinomethionate;dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate,and propineb; phenylcarbamate compounds such as diethofencarb;organochlorine compounds such as chlorothalonil and quintozene;benzimidazole compounds such as benomyl, thiophanate-methyl, andcarbendazole; phenylamide compounds such as metalaxyl, oxadixyl,ofurace, benalaxyl, furalaxyl, and cyprofuram; sulfenic acid compoundssuch as dichlofluanid; copper compounds such as copper hydroxide andoxine-copper; isoxazole compounds such as hydroxyisoxazole;organophosphorus compounds such as fosetyl-aluminium andtolclofos-methyl; N-halogenothioalkyl compounds such as captan,captafol, and folpet; dicarboxyimide compounds such as procymidone,iprodione, and vinchiozolin; benzanilide compounds such as flutolaniland mepronil; morpholine compounds such as fenproplmorph anddimethomorph; organotin compounds such as fenthin hydroxide, and fenthinacetate; and cyanopyrrole compounds such as fludioxonil and fenpiclonil.Other compounds usable herein include fthalide, fluazinam, cymoxanil,triforine, pyrifenox, fenarimol, fenpropidin, pencycuron, cyazofamid,iprovalicarb, and benthiavalicarb-isopropyl and the like.

According to another aspect of the present invention, there is provideduse of a compound represented by formula (I) or an agriculturally andhorticulturally acceptable salt thereof as a pest control agent.According to still another aspect of the present invention, there isprovided use of a compound represented by formula (Ia) or anagriculturally and horticulturally acceptable salt thereof as ahemipteran pest control agent. According to still another aspect of thepresent invention, there is provided use of a compound represented byformula (Ib) or an agriculturally and horticulturally acceptable saltthereof as a pest control agent.

EXAMPLES

The present invention is further illustrated by the following Examplesthat are not intended as a limitation of the invention. The compoundNos. correspond to the compound Nos. in Tables 1 to 14.

Example 1 Synthesis of Compound 73

Compound 76 (890 mg) synthesized by the method described in JapanesePatent Laid-Open Publication No. 259569/1996 was dissolved in an 80%aqueous methanol solution. Next, 1,8-diazabicyclo[5.4.0]-undeca-7-ene(216 mg) was added to the solution, and the mixture was stirred at roomtemperature for 1.5 hr. The reaction mixture was added with acetic acidto quench the reaction, and the solvent was removed by evaporation underthe reduced pressure. Water was added to the precipitated crystal,followed by extraction with chloroform. The chloroform layer was washedwith saturated brine, was dried over anhydrous magnesium sulfate, andthe solvent was removed by evaporation under the reduced pressure togive a crude product of compound 73. The crude product was purified bychromatography on silica gel (Mega Bond Elut (Varian),acetone:hexane=1:1) to give compound 73 (451 mg).

Mass spectrometric data (FAB⁺): 570(M+H)⁺

Example 2 Synthesis of Compound 218

Compound 102 (30 mg) synthesized by the method described in JapanesePatent Laid-Open Publication No. 259569/1996 and cyclopropanecarboxylicacid (112 mg) were dissolved in anhydrous N,N-dimethylformamide (2ml),and 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (76 mg)and 4-(dimethylamino)pyridine (32 mg) were added to the solution. Thereaction solution was stirred at room temperature for 68 hr and was thenpoured into water followed by extraction with ethyl acetate. The ethylacetate layer was washed with saturated brine and was dried overanhydrous magnesium sulfate, and the solvent was removed by evaporationunder the reduced pressure to give a crude product of compound 218. Thecrude product was purified by preparative thin-layer chromatography(Merck Silica Gel 60 F₂₅₄ 0.5 mm, acetone:hexane=1:1) to give compound218 (33 mg).

Mass spectrometric data (FAB⁺): 662(M+H)⁺

Example 3 Synthesis of Compound 261

Compound 218 (1.07 g), prepared in Example 2 was dissolved in an 80%aqueous methanol solution. 1,8-Diazabicyclo[5.4.0]-undeca-7-ene (271 mg)was added to the solution, and the mixture was stirred at roomtemperature for 24.5 hr. The reaction mixture was added with acetic acidto quench the reaction, and the solvent was removed by evaporation underthe reduced pressure. Water was added to the precipitated crystal,followed by extraction with chloroform. The chloroform layer was washedwith saturated brine and was dried over anhydrous magnesium sulfate, andthe solvent was removed by evaporation under the reduced pressure togive a crude product of compound 261. The crude product was purified bychromatography on silica gel (Mega Bond Elut (Varian),acetone:hexane=1:1) to give compound 261 (233 mg).

Mass spectrometric data (ESI⁺): 594(M+H)⁺

Example 4 Synthesis of Compound 222

Compound 73 (30 mg) prepared in Example 1 and4-(trifluoromethyl)nicotinic acid (30 mg) was dissolved in anhydrousN,N-dimethylformamide (3 ml). Next,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (15 mg) and4-(dimethylamino)pyridine (4 mg) were added to the solution, and thereaction solution was stirred at room temperature for 15 hr and was thenpoured into water, followed by extraction with ethyl acetate. The ethylacetate layer was washed with saturated brine and was dried overanhydrous magnesium sulfate, and the solvent was removed by evaporationunder the reduced pressure to give a crude produce of compound 222. Thecrude product was purified by preparative thin-layer chromatography(Merck Silica Gel 60 F₂₅₄ 0.5 mm, acetone:hexane=1:1) to give compound222 (19 mg).

Mass spectrometric data (FAB⁺): 743(M+H)⁺

Example 5 Synthesis of Compound 269

Compound 261 (20 mg) prepared in Example 3 and 2-cyanobenzoic acid (30mg) were dissolved in anhydrous N,N-dimethylformamide (1 ml), and1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (26 mg) and4-(dimethylamino)pyridine (4 mg) were added to the solution. Thereaction solution was stirred at room temperature for 12 hr, and thereaction solution was added to water, followed by extraction with ethylacetate. The ethyl acetate layer was washed with saturated brine and wasdried over anhydrous magnesium sulfate. The solvent was removed byevaporation under the reduced pressure to give a crude product ofcompound 269. The crude product was purified by preparative thin-layerchromatography (Merck Silica Gel 80 F₂₅₄ 0.5 mm, acetone:hexane=1:1) togive compound 269 (18 mg).

Mass spectrometric data (ESI⁺): 723 (M+H)⁺

Example 6 Synthesis of Compound 225

1,7,11-Trideacetyl-13-Oxo-6″-chloropyripyropene A (10 mg) described inJournal of Antibiotics (1997), 50 (3), 229-38 was dissolved in anhydrousN,N-dimethylformamide (1 ml). Triethylamine (24 mg) and4-(dimethylamino)pyridine (0.5 mg) were added to the solution, and themixture was stirred at room temperature for 30 min. Thereafter,propionic acid anhydride (8 mg) was added. The reaction solution wasstirred at the same temperature for 4 hr. The reaction solution wasadded to water, and the mixture was extracted with ethyl acetate. Theethyl acetate layer was washed with saturated brine and was dried overanhydrous magnesium sulfate, and the solvent was then removed byevaporation under the reduced pressure to give a crude product ofcompound 225. The crude product was purified by preparative thin-layerchromatography (Merck Silica Gel 60 F₂₅₄ 0.5 mm, acetone:hexane=1:1) togive compound 225 (5.6 mg).

Mass spectrometry data (ESI⁺): 658 (M+H)⁺

Example 7 Synthesis of Compound 226

Compound 225 (10 mg) prepared in Example 8 was dissolved in methanol (1ml), Cerium(III) chloride heptahydrate (57 mg) and sodium borohydride (6mg) were added to the solution. The mixture was stirred at 0° C. for 7hr, and water was added to the reaction solution, followed by extractionwith ethyl acetate. The ethyl acetate layer was washed with saturatedbrine and was dried over anhydrous magnesium sulfate, and the solventwas removed by evaporation under the reduced pressure to give a crudeproduct of compound 226. The crude product was purified by preparativethin-layer chromatography (Merck Silica Gel 60 F₂₅₄ 0.5 mm.acetone:hexane=1:1) to give compound 226 (8.5 mg).

Mass spectrometry data (ESI⁺): 660 (M+H)⁺

Example 8 Synthesis of Compound 273

1,7,11 -Trideacetyl-1,11-o-p-methoxybenzylidene pyripyropene A (10 mg)described in Japanese Patent Laid-Open Publication No. 269065/1996 wasdissolved in anhydrous dichloromethane (0.5 ml), and pyridiniumdichromate (PDC) (39 mg) was added to the solution. The reactionsolution was stirred at room temperature for 4 hr. and the reactionsolution was added to water. The dichloromethane layer was washed withsaturated brome, and was dried over anhydrous sodium sulfate, and thesolvent was then removed by evaporation under the reduced pressure togive a crude product of compound 273. The crude product was purified bypreparative thin-layer chromatography (Merck Silica Gel 60 F₂₅₄ 0.5 mm,chloroform:methanol=12.5:1) to give compound 273 (4.4 mg).

Mass spectrometric data (ESI⁺): 574 (M+H)⁺

Example 9 Synthesis of Compound 274

1,11-o-Cyclic carbonate 1,7,11 -trideacetyl-pyripyropene A (4 mg)described in Japanese Patent Laid-Open Publication No. 269085/1996 wasdissolved in anhydrous dichloromethane (1 ml). Triethylamine (5 μl) and4-(dimethylamino)pyridine (1 mg) were added to the solution. Thereaction solution was stirred at room temperature for 30 min, andvaleric acid anhydride (5 μl) was added thereto. Next, the reactionsolution was stirred at room temperature for 3 hr. The reaction solutionwas added to water, and the dichloromethane layer was washed withsaturated brine and was dried over anhydrous sodium sulfate. The solventwas then removed by evaporation under the reduced pressure to give acrude product of compound 274. The crude product was purified bypreparative thin-layer chromatography (Merck Silica Gel 60 F₂₅₄ 0.5 mm,chloroform:methanol=25:1) to give compound 274 (0.1 mg).

Mass spectrometric data (ESI⁺): 652 (M+H)⁺

Example 10

Compounds shown in Tables 15 to 17 were synthesized using startingmaterials, reaction reagents 1 and 2 and solvents described in thesetables. Further, the ¹H-NMR data about some of the compounds in Tables15 to 17 was described in Tables 18 to 29. In addition, CDCl₃ was usedas the solvent for the ¹H-NMR measurement. Tetramethylsilane was used asa standard substance for the ¹H-NMR measurement.

TABLE 15 Compound Starting material No. (Compound No.) Amount Reactionreagent 1 Amount Reaction reagent 2 74 73 30 mg acetic anhydride 32.7 mgEt₃N 64.0 mg, DMAP 12.8 mg 77 73 30 mg benzoic acid 84.8 mg EDCI 49.2mg, DMAP 46.4 mg 91 102 30 mg pivalic anhydride 220 mg Et₃N 60.0 mg,DMAP 8.0 mg 205 73 30 mg nicotinic acid 12.9 mg EDCI 15.1 mg, DMAP 6.4mg 206 73 30 mg isobutyric anhydride 50.0 mg Et₃N 64.0 mg, DMAP 12.8 mg207 73 30 mg pivalic anhydride 58.9 mg Et₃N 64.0 mg, DMAP 12.8 mg 208 7330 mg 4-(trifluoromethyl)benzoic anhydride 114 mg Et₃N 64.0 mg, DMAP12.8 mg 209 73 40 mg 1,1-carbonyl diimidazole 34.0 mg — 210 73 30 mgpropyl isocyanate 26.9 mg Et₃N 64.0 mg, DMAP 12.8 mg 211 73 30 mg3,4-dihydro-2H-pyran 155 mg pyridine hydrochloride 212 73 30 mg 6-chloronicotinic acid 16.5 mg EDCI 15.2 mg, DMAP 6.4 mg 213 73 30 mgcyclopropane carboxylic acid 27 mg EDCI 15.2 mg, DMAP 6.4 mg 214 73 30mg cyclobutane carboxylic acid 31 mg EDCI 15.2 mg, DMAP 6.4 mg 215 73 30mg acrylic acid 22.5 mg EDCI 15.2 mg, MAP 6.4 mg 216 73 30 mgisonicotinic acid 12.9 mg EDCI 15.2 mg, DMAP 6.4 mg 217 73 30 mgpicolinic acid 12.9 mg EDCI 15.2 mg, DMAP 6.4 mg 219 102 30 mgcyclobutane carboxylic acid 131 mg EDCI 76 mg, DMAP 32 mg 220 102 30 mgbenzoic acid 160 mg EDCI 126 mg, DMAP 80 mg 221 73 30 mg6-(trifluoromethyl)nicotinic acid 30 mg EDCI 15.2 mg, DMAP 6.4 mg 223102 30 mg 3,3,3-trifluoropropionic acid 168 mg EDCI 126 mg, DMAP 80 mg224 73 30 mg 3,3,3-trifluoropropionic acid 20 mg EDCI 15.2 mg, DMAP 6.4mg Compound Mass spectrometric data No. Solvent Yield Measuring MethodData 74 DMF 13.6 mg FAB 612 (M + H)⁺ 77 DMF 36.4 mg FAB 674 (M + H)⁺ 91DMF 27.7 mg FAB 710 (M + H)⁺ 205 DMF 27.1 mg FAB 675 (M + H)⁺ 206 DMF11.4 mg FAB 640 (M + H)⁺ 207 DMF 23.4 mg FAB 654 (M + H)⁺ 208 DMF 32.2mg FAB 742 (M + H)⁺ 209 toluene 5.1 mg FAB 664 (M + H)⁺ 210 DMF 3.2 mgFAB 655 (M + H)⁺ 211 CH₂Cl₂ 22.7 mg FAB 654 (M + H)⁺ 212 DMF 39.8 mg FAB709 (M + H)⁺ 213 DMF 18.2 mg FAB 638 (M + H)⁺ 214 DMF 14.9 mg FAB 652(M + H)⁺ 215 DMF 5.6 mg FAB 624 (M + H)⁺ 216 DMF 8.2 mg FAB 675 (M + H)⁺217 DMF 40.6 mg FAB 675 (M + H)⁺ 219 DMF 38.9 mg FAB 704 (M + H)⁺ 220DMF 37.9 mg FAB 770 (M + H)⁺ 221 DMF 35.4 mg FAB 743 (M + H)⁺ 223 DMF10.4 mg FAB 788 (M + H)⁺ 224 DMF 8.0 mg FAB 680 (M + H)⁺

TABLE 16 Compound Starting material No. (Compound No.) Amount Reactionreagent 1 Amount Reaction reagent 2 227 73 20 mg 3-fluoro-isonicotinicacid 15 mg EDCI 14 mg, DMAP 4 mg 228 73 20 mg 3-chloro-isonicotinic acid17 mg EDCI 14 mg, DMAP 4 mg 229 73 20 mg 3-methylpicolinic acid 14 mgEDCI 28 mg, DMAP 8 mg 230 73 20 mg 3-benzoyl-2-pyridine 48 mg EDCI 28mg, DMAP 8 mg carboxylic acid 231 73 20 mg 3-n-propoxy picolinic acid 38mg EDCI 28 mg, DMAP 8 mg 232 73 20 mg 6-fluoro nicotinic acid 30 mg EDCI28 mg, DMAP 8 mg 233 102 20 mg cyclopentane carboxylic acid 99 mg EDCI84 mg, DMAP 5 mg 234 102 20 mg cyclohexane carboxylic acid 112 mg EDCI84 mg, DMAP 5 mg 235 102 20 mg cyano acetic acid 74 mg EDCI 84 mg, DMAP5 mg 236 102 20 mg cyclopropylacetic acid 87 mg EDCI 84 mg, DMAP 5 mg237 102 20 mg cyclopropylacetic acid 87 mg EDCI 84 mg, DMAP 5 mg 238 10220 mg 2,2-difluoro-1-methylcyclo- 118 mg EDCI 84 mg, DMAP 5 mgpropanecarboxylic acid 239 73 20 mg 4-methylnicotinic acid 36 mg EDCI 28mg, DMAP 8 mg 240 73 20 mg 4-chloro nicotinic acid 33 mg EDCI 28 mg,DMAP 8 mg 241 73 20 mg (4-methoxy carbonyl) nicotinic acid 38 mg EDCI 28mg, DMAP 8 mg 242 73 20 mg 5-(trifluoromethyl)thieno[3,2- 38 mg EDCI 28mg, DMAP 8 mg b]pyridine-6-carboxylic acid 243 73 20 mg 2-cyano benzoicacid 31 mg EDCI 28 mg, DMAP 8 mg 244 73 20 mg 2-(trifluoromethyl)benzoicacid 40 mg EDCI 28 mg, DMAP 8 mg 245 73 20 mg 2-fluoro benzoic acid 29mg EDCI 28 mg, DMAP 8 mg 246 73 20 mg 2-nitro benzoic acid 35 mg EDCI 28mg, DMAP 8 mg 247 73 20 mg 2-chloro nicotinic acid 33 mg EDCI 28 mg,DMAP 8 mg Compound Mass spectrometric data No. Solvent Yield MeasuringMethod Data 227 DMF 5.4 mg FAB 693 (M + H)⁺ 228 DMF 7.8 mg FAB 709 (M +H)⁺ 229 DMF 16.7 mg FAB 689 (M + H)⁺ 230 DMF 16.4 mg FAB 779 (M + H)⁺231 DMF 17.3 mg FAB 733 (M + H)⁺ 232 DMF 5.3 mg FAB 693 (M + H)⁺ 233 DMF28.3 mg FAB 746 (M + H)⁺ 234 DMF 21.5 mg FAB 788 (M + H)⁺ 235 DMF 3.3 mgFAB 659 (M + H)⁺ 236 DMF 16.7 mg FAB 786 (M + H)⁺ 237 DMF 8.2 mg FAB 704(M + H)⁺ 238 DMF 6.1 mg FAB 812 (M + H)⁺ 239 DMF 16.1 mg FAB 689 (M +H)⁺ 240 DMF 13.8 mg FAB 709 (M + H)⁺ 241 DMF 18.8 mg FAB 733 (M + H)⁺242 DMF 20.3 mg FAB 799 (M + H)⁺ 243 DMF 6.6 mg FAB 699 (M + H)⁺ 244 DMF10.2 mg FAB 742 (M + H)⁺ 245 DMF 16.1 mg FAB 692 (M + H)⁺ 246 DMF 9.8 mgFAB 719 (M + H)⁺ 247 DMF 13.1 mg FAB 709 (M + H)⁺

TABLE 17 Compound Starting material No. (Compound No.) Amount Reactionreagent 1 Amount Reaction reagent 2 248 73 20 mg2-chloro-6-methylnicotinic acid 36 mg EDCI 28 mg, DMAP 8 mg 249 73 20 mgmethoxymethyl bromide 31 mg [(CH₃)₂CH]₂NEt 18 mg 250 102 20 mg2,2-difluorocyclopropane carboxylic acid 106 mg EDCI 84 mg, DMAP 5 mg251 73 20 mg 3-tert-buthylthio-2-carboxy piridine 44 mg EDCI 28 mg, DMAP8 mg 252 73 20 mg 3,5-difluoropyridine-2-carboxylic acid 33 mg EDCI 28mg, DMAP 8 mg 253 73 20 mg pyrazine carboxylic acid 26 mg EDCI 28 mg,DMAP 8 mg 254 73 20 mg 4-thiazole carboxylic acid 27 mg EDCI 28 mg, DMAP8 mg 255 73 20 mg 3-chloro thiophene-2-carboxylic acid 34 mg EDCI 28 mg,DMAP 8 mg 256 73 20 mg 6-methylnicotinic acid 29 mg EDCI 28 mg, DMAP 8mg 257 73 20 mg 6-chloro pyridine-2-carboxylic acid 33 mg EDCI 28 mg,DMAP 8 mg 258 73 20 mg 6-fluoro pyridine-2-carboxylic acid 30 mg EDCI 28mg, DMAP 8 mg 259 73 20 mg 1-methyl indole-2-carboxylic acid 37 mg EDCI28 mg, DMAP 8 mg 260 73 20 mg 3-chloropyridine-2-carboxylic acid 33 mgEDCI 28 mg, DMAP 8 mg 262 73 20 mg 2-fluoro nicotinic acid 30 mg EDCI 28mg, DMAP 8 mg 263 73 20 mg 4-cyano benzoic acid 31 mg EDCI 28 mg, DMAP 8mg 264 73 20 mg 3-cyano benzoic acid 31 mg EDCI 28 mg, DMAP 8 mg 265 7320 mg 3-(trifluoromethyl)benzoic acid 40 mg EDCI 28 mg, DMAP 8 mg 266 7320 mg 2-pyridylacetic acid 36 mg EDCI 28 mg, DMAP 8 mg 267 73 20 mg3-pyridylacetic acid 36 mg EDCI 28 mg, DMAP 8 mg 268 73 20 mg(4-pyridylthio) acetic acid 36 mg EDCI 28 mg, DMAP 4 mg 270 261 20 mg4-(trifluoromethyl)nicotinic acid 39 mg EDCI 26 mg, DMAP 4 mg 271 261 20mg 3-chloropyridine-2-carboxylic acid 32 mg EDCI 26 mg, DMAP 4 mgCompound Mass spectrometric data No. Solvent Yield Measuring Method Data248 DMF 17.2 mg FAB 723 (M + H)⁺ 249 DMF 1.2 mg ESI 614 (M + H)⁺ 250 DMF23.2 mg ESI 770 (M + H)⁺ 251 DMF 7.6 mg ESI 763 (M + H)⁺ 252 DMF 10.9 mgESI 711 (M + H)⁺ 253 DMF 10.9 mg ESI 676 (M + H)⁺ 254 DMF 18.5 mg ESI681 (M + H)⁺ 255 DMF 15.8 mg ESI 714 (M + H)⁺ 256 DMF 15.1 mg ESI 689(M + H)⁺ 257 DMF 12.7 mg ESI 709 (M + H)⁺ 258 DMF 14.4 mg ESI 693 (M +H)⁺ 259 DMF 18.8 mg ESI 727 (M + H)⁺ 260 DMF 14.6 mg ESI 709 (M + H)⁺262 DMF 9.9 mg ESI 693 (M + H)⁺ 263 DMF 14.0 mg ESI 699 (M + H)⁺ 264 DMF16.9 mg ESI 699 (M + H)⁺ 265 DMF 14.3 mg ESI 742 (M + H)⁺ 266 DMF 11.7mg ESI 689 (M + H)⁺ 267 DMF 8.6 mg ESI 689 (M + H)⁺ 268 DMF 16.5 mg ESI721 (M + H)⁺ 270 DMF 8.3 mg ESI 767 (M + H)⁺ 271 DMF 14.5 mg ESI 733(M + H)⁺

TABLE 18 Compound No. ¹H-NMR δ (ppm) 73 0.91 (3H, s), 1.13 (3H, t, J =5.1 Hz), 1.14 (3H, t, J = 5.1 Hz), 1.26 (1H, s), 1.32-1.40 (1H, m), 1.42(3H, s), 1.45 (1H, d, J = 2.7 Hz), 1.49-1.51 (2H, m), 1.66 (3H, s),1.81-1.91 (2H, m), 2.13-2.18 (1H, m), 2.24-2.37 (4H, m), 2.90 (1H, m),3.79 (3H, m), 4.80 (1H, dd, J = 3.5, 7.6 Hz), 4.99-5.00 (1H, m), 6.52(1H, s), 7.42 (1H, dd, J = 3.5, 5.4 Hz), 8.11 (1H, dt, J = 1.4, 5.4 Hz),8.70 (1H, d, J = 2.4 Hz), 9.00 (1H, s) 77 0.92 (3H, s), 1.14 (3H, t, J =7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 1.26 (1H, s), 1.37-1.46 (1H, m), 1.51(3H, s), 1.62 (1H, d, J = 3.8 Hz), 1.68-1.82 (2H, m), 1.87 (3H, s),1.91-2.00 (2H, m), 2.18-2.23 (1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.43(2H, dq, J = 1.4, 7.6 Hz), 2.97 (1H, s), 3.70 (1H, d, J = 11.9 Hz), 3.84(1H, d, J = 11.9 Hz), 4.83 (1H, dd, J = 5.1, 11.1 Hz), 5.05 (1H, d, J =4.3 Hz), 5.27 (1H, dd, J = 4.6, 11.1 Hz), 6.45 (1H, s), 7.39-7.66 (4H,m), 8.05- 8.13 (3H, m), 8.70 (1H, d, J = 4.6 Hz), 9.00 (1H, s) 74 0.90(3H, s), 1.12 (3H, t, J = 7.8 Hz), 1.13 (3H, t, J = 7.8 Hz), 1.19 (1H,s), 1.25-1.34 (1H, m), 1.44 (3H, s), 1.53-1.63 (3H, m), 1.69 (3H, s),1.73-1.90 (2H, m), 2.10 (1H, m), 2.16 (3H, s), 2.33 (2H, dq, J = 24, 7.6Hz), 2.36 (2H, dq, J = 3.2, 7.6 Hz), 2.87 (1H, m), 3.72 (2H, m), 4.81(1H, dd, J = 4.6, 11.6 Hz), 4.97-5.00 (2H, m), 6.46 (1H, s), 7.40 (1H,dd, J = 4.6, 8.1 Hz), 8.10 (1H, m), 8.69 (1H, d, J = 4.9 Hz), 9.00 (1H,s) 205 0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz),1.26 (1H, s), 1.42-1.50 (1H, m), 1.59 (3H, s), 1.61-1.83 (3H, m), 1.85(3H, s), 1.83-2.00 (2H, m), 2.18-2.23 (1H, m), 2.33 (2H, q, J = 7.6 Hz),2.43 (2H, q, J = 7.6 Hz), 2.94 (1H, m), 3.72 (1H, d, J = 11.9 Hz), 3.82(1H, d, J = 12.7 Hz), 4.83 (1H, dd, J = 4.9, 11.3 Hz), 5.03-5.06 (1H,m), 5.27 (1H, dd, J = 4.9, 11.3 Hz), 6.42 (1H, s), 7.38 (1H, dd, J =4.9, 8.1 Hz), 7.45 (1H, dd, J = 4.9, 8.1 Hz), 8.07 (1H, dt, J = 2.2, 8.1Hz), 8.36 (1H, dt, J = 1.9, 8.1 Hz), 8.67 (1H, dd, J = 1.9, 5.1 Hz),8.83 (1H, dd, J = 1.9, 4.9 Hz), 8.97 (1H, d, J = 1.9 Hz), 9.30 (1H, d, J= 1.9 Hz) 206 0.90 (3H, s), 1.13 (6H, t, J = 7.6 Hz), 1.19 (1H, s), 1.24(3H, d, J = 4.6 Hz), 1.26 (3H, d, J = 4.6 Hz), 1.33-1.38 (1H, m), 1.45(3H, s), 1.54 (1H, d, J = 3.8 Hz), 1.60-1.64 (2H, m), 1.67 (3H, s),1.75-1.90 (2H, m), 2.15-2.19 (1H, m), 2.32 (2H, q, J = 7.6 Hz), 2.38(2H, q, J = 7.6 Hz), 2.65 (1H, quint, J = 7.6 Hz), 2.88 (1H, d, J = 1.6Hz), 3.68 (1H, d, J = 12.4 Hz), 3.83 (1H, d, J = 11.9 Hz), 4.80 (1H, dd,J = 4.9, 11.3 Hz), 5.00 (2H, m), 6.38 (1H, s), 7.40 (1H, dd, J = 4.6,8.1 Hz), 8.09, (1H, dt, J = 1.9, 8.1 Hz), 8.69 (1H, dd, J = 1.6, 4.6Hz), 9.00 (1H, d, J = 1.6 Hz)

TABLE 19

¹H-NMR δ (ppm) 208 0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.21 (3H, t,J = 7.6 Hz), 1.26 (1H, s), 1.39-1.47 (1H, m), 1.50 (3H, s), 1.61 (1H,m), 1.68-1.83 (2H, m), 1.86 3H, s), 1.91-2.05 (2H, m), 2.18-2.23 (1H,m), 2.33 (2H, q, J = 7.6 Hz), 2.43 (2H, dq, J = 1.4, 7.6 Hz), 2.95 (1H,d, J = 2.4 Hz), 3.72 (1H, d, J = 11.9 Hz), 3.82 (1H, d, J = 11.9 Hz),4.83 (1H, dd, J = 5.1, 11.1 Hz), 5.03-5.06 (1H, m), 5.26 (1H, dd, J =4.9, 11.1 Hz), 6.40 (1H, s), 7.38 (1H, dd, J - 4.9, 8.4 Hz), 7.76 (2H,d, J = 8.4 Hz), 8.06 (1H, dt, J = 2.2, 8.1 Hz), 8.22 (2H, d, J = 8.4Hz), 8.66 (1H, dd, J = 1.6, 4.9 Hz), 8.96 (1H, d, J = 2.2 Hz) 211 0.90(3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.15 (3H, t, J = 7.6 Hz), 1.26 (1H,s), 1.29-1.38 (1H, m), 1.41 (3H, s), 1.43-1.71 (5H, m), 1.59 (3H, s),1.75-1.89 (6H, m), 2.12-2.17 (1H, m), 2.26-2.38 (4H, m), 2.86 (1H, m),3.45-4.00 (5H, m), 4.82 (1H, dd, J = 5.4, 10.8 Hz), 4.97-5.03 (2H, m),6.41 (1H, s), 7.40 (1H, dd, J = 4.9, 7.8 Hz), 8.07-8.13 (1H, m),8.67-8.70 (1H, m), 9.01 (1H, d, J = 2.4 Hz) 212 0.92 (3H, s), 1.14 (3H,t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 1.26 (1H, s), 1.38-1.46 (1H,m), 1.50 (3H, s), 1.61 (1H, m), 1.66-1.78 (2H, m), 1.84 (3H, s),1.87-1.99 (2H, m), 2.12-2.23 (1H, m), 2.31 (2H, q. J = 7.6 Hz), 2.41(2H, q, J = 7.6 Hz), 2.95 (1H, m), 3.73 (1H, d, J = 11.9 Hz), 3.81 (1H,d, J = 11.9 Hz), 4.83 (1H, dd, J = 4.9, 11.3 Hz), 5.04 (1H, m), 5.25(1H, dd, J = 4.9, 11.3 Hz), 6.40 (1H, s), 7.38 (1H, dd, J = 4.6, 7.8Hz), 7.47 (1H, d, J = 8.1 Hz), 8.06 (1H, dt, J = 1.6, 7.8 Hz), 8.30 (1H,dd, J = 2.4, 8.1 Hz), 8.67 (1H, dd, J = 1.4, 4.6 Hz), 8.97 (1H, d, J =2.4 Hz), 9.06 (1H, d, J = 2.7 Hz) 213 0.90 (3H, s), 0.93 (2H, d, J = 2.7Hz), 0.96 (2H, d, J = 2.7 Hz), 1.03-1.19 (6H, m), 1.26 (1H, s),1.32-1.39 (1H, m), 1.45 (3H, s), 1.52 (1H, d, J = 3.8 Hz), 1.61-1.69(3H, m), 1.71 (3H, s), 1.73-1.94 (2H, m), 2.14-2.19 (1H, m), 2.24-2.40(4H, m), 2.95 (1H, m), 3.68 (1H, d, J = 11.9 Hz), 3.81 (1H, d, J = 11.9Hz), 4.79 (1H, dd, J = 5.4, 11.3 Hz), 4.96-5.00 (2H, m), 6.45 (1H, s),7.40 (1H, dd, J = 4.6, 8.1 Hz), 8.10 (1H, dt, J = 1.9, 8.1 Hz), 8.68(1H, m), 9.01 (1H, m) 214 0.90 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.17(3H, t, J = 7.6 Hz), 1.26 (1H, s), 1.34-1.40 (1H, m), 1.44 (3H, s), 1.54(1H, d, J = 4.3 Hz), 1.61 - 1.67 (2H, m), 1.69 (3H, s), 1.72-2.42 (13H,m), 2.91 (1H, m), 3.23 (1H, quint, J = 8.1 Hz), 3.69 (1H, d, J = 11.9Hz), 3.81 (1H, d, J = 11.9 Hz), 4.80 (1H, dd, J = 4.9, 11.3 Hz),4.99-5.04 (2H, m), 6.40 (1H, s), 7.39 (1H, dd, J = 4.9, 8.1 Hz), 8.09(1H, dt, J = 1.6, 8.1 Hz), 8.69 (1H, dd, J = 1.6, 4.6 Hz), 9.01 (1H, d,J = 1.6 Hz) 215 0.90 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.17 (3H, t, J =7.6 Hz), 1.26 (1H, s), 1.41-1.46 (1H, m), 1.59 (3H, s), 1.65-1.68 (3H,m), 1.73 (3H, s), 1.84-1.90 (2H, m), 2.18 (1H, m), 2.31 (2H, q, J = 7.6Hz), 2.38 (2H, q, J = 7.6 Hz), 2.93 (1H, m), 3.69 (1H, d, J = 11.9 Hz),3.81 (1H, d, J = 11.9 Hz), 4.80 (1H, m), 5.01-5.09 (2H, m), 5.92 (1H,dd, J = 1.6, 10.5 Hz), 6.15-6.24 (1H, m), 6.45 (1H, s), 6.45-6.53 (1H,m), 7.40 (1H, dd, J = 4.6, 7.8 Hz), 8.07-8.11 (1H, m), 8.68 (1H, dd, J =1.9, 4.9 Hz), 9.00 (1H, d, J = 22 Hz)

TABLE 20

¹H-NMR δ (ppm) 216 0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t,J = 7.6 Hz), 1.26 (1H, s), 1.38-1.42 (1H, m), 1.50 (3H, s), 1.64-1.78(3H, m), 1.85 (3H, s), 1.88-2.08 (2H, m), 2.17-2.23 (1H, m), 2.33 (2H,q, J = 7.6 Hz), 2.42 (2H, dq, J = 1.1, 7.6 Hz), 2.99 (1H, m), 3.72 (1H,d, J = 12.4 Hz), 3.81 (1H, d, J = 11.5 Hz), 4.83 (1H, dd, J = 4.9, 11.5Hz), 5.03-6.05 (1H, m), 5.25 (1H, dd, J = 5.4, 11.5 Hz), 6.41 (1H, s),7.37 (1H, dd, J = 5.2, 8.1 Hz), 7.91 (2H, dd, J = 1.6,4.6 Hz), 8.07 (1H,dt, J = 1.6, 8.1 Hz), 8.67 (1H, dd, J = 1.9, 4.9 Hz), 8.83 (2H, dd, J =1.6, 4.3 Hz), 8.97 (1H, d, J = 1.6 Hz) 217 0.91 (3H, s), 1.13 (3H, t, J= 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 1.26 (1H, s), 1.37-1.46 (1H, m),1.50 (3H, s), 1.63-1.75 (3H, m), 1.87 (3H, s), 1.83-1.96 (2H, m),2.13-2.23 (1H, m), 2.32 (2H, q, J = 7.6 Hz), 2.41 (2H, dq, J = 1.4, 7.6Hz), 2.99 (1H, m), 3.67 (1H, d, J = 11.9 Hz), 3.83 (1H, d, J = 11.9 Hz),4.83 (1H, dd, J = 5.4, 11.3 Hz), 4.98-5.06 (1H, m), 5.38 (1H, dd, J =5.4, 10.8 Hz), 6.43 (1H, s), 7.36-7.44 (1H, m), 7.50-7.56 (1H, m), 7.89(1H, dt, J = 1.6, 7.6 Hz), 8.07 (1H, dt, J = 1.6, 8.1 Hz), 8.18 (1H, d,J = 7.6 Hz), 8.67 (1H, dd, J = 1.6, 4.9 Hz), 8.82-8.84 (1H, m), 8.97(1H, d, J = 2.4 Hz) 218 0.83-1.12 (12H, m), 0.91 (3H, s), 1.26 (1H, s),1.33-1.41 (1H, m), 1.45 (3H, s), 1.52-1.69 (6H, m), 1.71 (3H, s),1.81-1.93 (2H, m), 2.14-2.18 (1H, m), 2.92 (1H, m), 3.72 (1H, d, J =11.9 Hz), 3.82 (1H, d, J = 11.9 Hz), 4.80 (1H, dd, J = 4.9, 11.4 Hz),4.99-5.04 (2H, m), 6.46 (1H, s), 7.41 (1H, dd, J = 4.9, 8.3 Hz), 8.10(1H, dt, J = 1.7, 8.3 Hz), 8.69 (1H, dd, J = 1.5, 4.9 Hz), 9.01 (1H, d,J = 1.4 Hz) 219 0.90 (3H, s), 1.26 (1H, s), 1.32-1.41 (1H, m), 1.44 (3H,s), 1.51-1.63 (3H, m), 1.69 (3H, s), 1.79-2.04 (8H, m), 2.17-2.40 (14H,m), 2.89 (1H, m), 3.08-3.26 (3H, m), 3.67 (1H, d, J = 11.9 Hz), 3.78(1H, d, J = 11.9 Hz), 4.79 (1H, dd, J = 5.4, 11.1 Hz), 4.97-5.00 (2H,m), 6.41 (1H, s), 7.41 (1H, dd, J = 4.9, 8.1 Hz), 8.09 (1H, dt, J = 1.9,8.4 Hz), 8.68 (1H, m), 9.00(1H, m) 220 1.17 (3H, s), 1.26 (1H, s), 1.57(3H, s), 1.65 (1H, m), 1.77- 1.82 (2H, m), 1.88 (3H, s), 1.94-2.05 (3H,m), 2.13-2.31 (1H, m), 2.95 (1H, m), 4.16 (2H, s), 5.06 (1H, dd, J =2.4, 6.5 Hz), 5.17-5.32 (2H, m), 6.42 (1H, s), 7.34-7.64 (10H, m), 8.01-8.12 (7H, m), 8.66 (1H, dd, J = 1.6, 5.1 Hz), 8.97 (1H, d, J = 1.9 Hz)221 0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.21 (3H, t, J = 7.6 Hz),1.26 (1H, s), 1.44 (1H, m), 1.50 (3H, s), 1.57-1.62 (1H, m), 1.67-1.80(2H, m), 1.85 (3H, s), 1.91-1.95 (2H, m), 2.17-2.24 (1H, m), 2.33 (2H,q, J = 7.6 Hz), 2.42 (2H, q, J = 7.6 Hz), 2.92 (1H, m), 3.74 (1H, d, J =11.9 Hz), 3.81 (1H, dd, J = 11.9 Hz), 4.84 (1H, dd, J = 4.9, 11.1 Hz),5.04 (1H, m), 5.27 (1H, dd, J = 4.9, 11.1 Hz), 6.40 (1H, s), 7.38 (1H,dd, J = 4.9, 8.1 Hz), 7.84 (1H, d, J = 8.4 Hz), 8.05-8.08 (1H, m), 8.64(1H, d, J = 8.1 Hz), 8.67 (1H, d, J = 4.6 Hz), 8.96 (1H, d, J = 2.2 Hz),9.38 (1H, s)

TABLE 21

¹H-NMR δ (ppm) 222 0.94 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t,J = 7.6 Hz), 1.26 (1H, s), 1.38-1.47 (1H, m), 1.48 (3H, s), 1.57-1.71(3H, m), 1.76 (3H, s), 1.83-1.97 (2H, m), 2.10-2.22 (1H, m), 2.33 (2H,q, J = 7.6 Hz), 2.41 (2H, dq, J = 1.6, 7.6 Hz), 2.96 (1H, m), 3.74-3.80(2H, m), 4.83 (1H, dd, J = 5.7, 11.6 Hz), 5.02- 5.03 (1H, m), 5.28 (1H,dd, J = 5.4, 11.6 Hz), 6.41 (1H, s), 7.40 (1H, dd, J = 5.4, 7.6 Hz),7.69 (1H, d, J = 5.4 Hz), 8.08 (1H, dt, J = 2.2, 8.1 Hz), 8.69 (1H, dd,J = 1.6, 4.9 Hz), 8.97 (1H, d, J = 4.6 Hz), 9.00 (1H, d, J = 2.4 Hz),9.16 (1H, s) 223 0.94 (3H, s), 1.26 (1H, s), 1.37 (1H, m), 1.47 (3H, s),1.48- 1.66 (3H, m), 1.71 (3H, s), 1.75-1.96 (2H, m), 2.17-2.24 (1H, m),2.96 (1H, m), 3.14-3.35 (6H, m), 3.86 (1H, d, J = 12.2 Hz), 3.93 (1H, d,J = 12.2 Hz), 4.87 (1H, dd, J = 5.7, 10.8 Hz), 4.99-5.08 (2H, m), 6.41(1H, s), 7.41 (1H, dd, J = 4.6, 8.1 Hz), 8.09 (1H, m), 8.69 (1H, m),9.02 (1H, m) 224 0.91 (3H, s), 1.13 (3H, t, J = 7.3 Hz), 1.17 (3H, t, J= 7.3 Hz), 1.26 (1H, s), 1.40 (1H, m), 1.45 (3H, s), 1.58-1.63 (3H, m),1.70 (3H, s), 1.73-1.89 (2H, m), 2.10-2.18 (1H, m), 2.32 (2H, q, J = 7.6Hz), 2.36 (2H, q, J = 7.6 Hz), 2.96 (1H, m), 3.25 (1H, d, J = 9.7 Hz),3.32 (1H, d, J = 9.7 Hz), 3.69-3.81 (2H, m), 4.80 (1H, dd, J = 6.4, 11.3Hz), 5.00-5.08 (2H, m), 6.40 (1H, s), 7.41 (1H, dd, J = 4.9, 8.1 Hz),8.09 (1H, m), 8.69 (1H, dd, J = 1.4, 5.1 Hz), 9.01 (1H, d, J = 2.4 Hz)225 0.88 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 7.5 Hz),1.22 (3H, t, J = 7.6 Hz), 1.24 (3H, s), 1.26 (1H, m), 1.50-1.56 (1H, m),1.56 (3H, s), 1.55-1.64 (3H, m), 1.70-1.84 (2H, m), 2.31 (2H, dq, J =1.2, 7.8 Hz), 2.42 (2H, dq, J = 3.4, 13.6 Hz), 2.44 (2H, dq, J = 2.0,7.5 Hz), 2.79 (1H, dt, J = 1.4, 5.1 Hz), 3.69 (1H, d, J = 11.9 Hz), 3.79(1H, d, J = 11.9 Hz), 4.79 (1H, dd, J = 4.9, 11.4 Hz), 5.24 (1H, dd, J =4.9, 11.4 Hz), 6.45 (1H, s), 7.47 (1H, d, J = 8.5 Hz), 8.12 (1H, dd, J =2.7, 8.5 Hz), 8.83 (1H, d, J = 2.7 Hz) 226 0.89 (3H, s), 1.13 (3H, t, J= 7.6 Hz), 1.19 (3H, t, J = 7.6 Hz), 1.10-1.24 (3H, m), 1.26 (1H, s),1.31-1.39 (1H, m), 1.44 (3H, s), 1.53 (1H, d, J = 3.8 Hz), 1.61-1.67(2H, m), 1.69 (3H, s), 1.72-1.92 (2H, m), 2.08-2.18 (1H, m), 2.31 (2H,dq, J = 2.7, 7.6 Hz), 2.44 (2H, dq, J = 1.6, 7.6 Hz), 2.26-2.64 (2H, m),2.85 (1H, s), 3.69 (1H, d, J = 11.9 Hz), 3.80 (1H, d, J = 11.9 Hz), 4.80(1H, dd, J = 5.4, 11.3 Hz), 4.92-5.10 (2H, m), 6.41 (1H, s), 7.44 (1H,d, J = 8.4 Hz), 8.05 (1H, dd, J = 2.4, 8.4 Hz), 8.78 (1H, d, J = 2.4 Hz)227 0.88 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz),1.23-1.33 (1H, m), 1.43 (1H, m), 1.49 (3H, s), 1.61-1.74 (3H, m), 1.82(3H, s), 1.87-2.23 (3H, m), 2.33 (2H, q, J = 7.6 Hz), 2.42 (2H, q, J =7.6 Hz), 2.96 (1H, m), 3.73 (1H, d, J = 12.4 Hz), 3.82 (1H, d, J = 12.4Hz), 4.83 (1H, dd, J = 5.4, 11.3 Hz), 5.03 (1H, m), 5.26 (1H, dd, J =5.4, 11.3 Hz), 6.43 (1H, s), 7.39 (1H, dd, J = 4.9, 8.1 Hz), 7.86 (1H,t, J = 5.4 Hz), 8.08 (1H, dt, J = 1.9, 7.8 Hz), 8.60 (1H, d, J = 2.2Hz), 8.66-8.68 (2H, m), 8.98 (1H, d, J = 2.2 Hz)

TABLE 22

¹H-NMR δ (ppm) 228 0.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t,J = 7.6 Hz), (1H, s), 1.32-1.44 (1H, m), 1.49 (3H, s), 1.61 (1H, d, J =4.1 Hz), 1.67-1.75 (2H, m), 1.81 (3H, s), 1.79-2.05 (2H, m), 2.13-2.22(1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 1.4, 7.6 Hz), 2.92(1H, m), 3.74 (1H, d, J = 11.9 Hz), 3.82 (1H, d, J = 11.9 Hz), 4.84 (1H,dd, J = 5.4, 10.8 Hz), 5.04 (1H, m), 5.27 (1H, dd, J = 5.4, 10.8 Hz),6.43 (1H, s), 7.40 (1H, dd, J = 4.9, 8.1 Hz), 7.74 (1H, d, J = 5.1 Hz),8.08 (1H, dt, J = 2.2, 8.1 Hz), 8.65 (1H, d, J = 4.9 Hz), 8.69 (1H, dd,J = 4.1, 7.6 Hz), 8.78 (1H, s), 8.99 (1H, d, J = 1.9 Hz) 229 0.92 (3H,s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 6.5 Hz), 1.26 (1H, s),1.34-1.45 (1H, m), 1.49 (3H, s), 1.62 (1H, m), 1.71-1.77 (2H, m), 1.83(3H, s), 1.88-2.01 (2H, m), 2.14-2.22 (1H, m), 2.33 (2H, q, J = 7.6 Hz),2.42 (2H, dq, J = 2.2, 7.6 Hz), 2.64 (3H, s), 2.96 (1H, m), 3.72 (1H, d,J = 11.9 Hz), 3.84 (1H, d, J = 11.9 Hz), 4.84 (1H, dd, J = 5.4, 11.3Hz), 5.04 (1H, m), 5.36 (1H, dd, J = 5.4, 10.8 Hz), 6.42 (1H, s),7.35-7.42 (2H, m), 7.66 (1H, d, J = 7.8 Hz), 8.08 (1H, dt, J = 1.9, 7.8Hz), 8.60 (1H, d, J = 4.1 Hz), 8.68 (1H, dd, J = 1.6, 4.9 Hz), 8.98 (1H,d, J = 2.4 Hz), 230 0.78 (3H, s), 1.09 (3H, t, J = 7.8 Hz), 1.12 (3H, t,J = 7.8 Hz), 1.26 (1H, s), 1.33 (3H, s), 1.36-1.38 (1H, m), 1.40-1.48(2H, m), 1.55 (3H, s), 1.59-1.85 (2H, m), 2.09-2.18 (1H, m), 2.32 (4H,q, J = 7.6 Hz), 2.96 (1H, m), 3.40 (1H, d, J = 11.9 Hz), 3.75 (1H, d, J= 11.9 Hz), 4.72 (1H, dd, J = 4.9, 11.3 Hz), 4.95 (1H, m), 5.17 (1H, dd,J = 5.4, 11.9 Hz), 6.45 (1H, s), 7.40 (1H, dd, J = 4.9, 8.1 Hz),7.49-7.67 (3H, m), 7.83-7.88 (3H, m), 8.02 (1H, s), 8.07 (1H, dt, J =2.2, 8.1 Hz), 8.68 (1H, dd, J = 1.4, 4.6 Hz), 8.95 (1H, dd, J = 1.6, 4.6Hz), 8.99 (1H, d, J = 1.9 Hz) 231 0.91 (3H, s), 1.09 (3H, t, J = 7.6Hz), 1.14 (3H, t, J = 7.6 Hz), 1.18 (3H, t, J = 7.6 Hz), 1.26 (1H, s),1.34-1.43 (1H, m), 1.48 (3H, s), 1.63 (1H, m), 1.67-1.75 (2H, m), 1.80(3H, s), 1.83- 2.08 (4H, m), 2.17-2.25 (1H, m), 2.32 (2H, q, J = 7.6Hz), 2.40 (2H, dq, J = 7.6, 1.9 Hz), 2.96 (1H, m), 3.64 (1H, d, J = 11.9Hz), 3.87 (1H, d, J = 11.9 Hz), 4.05 (2H, t, J = 6.2 Hz), 4.82 (1H, dd,J = 5.4, 10.8 Hz), 5.04 (1H, m), 5.40 (1H, dd, J = 5.4, 10.8 Hz), 6.47(1H, s), 7.19-7.44 (3H, m), 8.08 (1H, dt, J = 1.9, 8.1 Hz), 8.32 (1H,dd, J = 1.6, 4.3 Hz), 8.68 (1H, dd, J = 4.6, 1.6 Hz), 8.98 (1H, d, J =1.6 Hz) 232 0.92 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6Hz), 1.26 (1H, s), 1.34-1.43 (1H, m), 1.50 (3H, s), 1.61 (1H, m),1.67-1.78 (2H, m), 1.84 (3H, s), 1.87-1.97 (2H, m), 2.13-2.23 (1H, m),2.18 (1H, s), 2.32 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 1.4, 7.6 Hz),3.73 (1H, d, J = 11.9 Hz), 3.80 (1H, d, J = 11.9 Hz), 4.83 (1H, dd, J =5.4, 11.1 Hz), 5.04 (1H, d, J = 3.8 Hz), 5.25 (1H, dd, J = 5.1, 11.1Hz), 6.41 (1H, s), 7.06 (1H, dd, J = 3.0, 8.6 Hz), 7.38 (1H, dd, J =4.9, 8.1 Hz), 8.08 (1H, dt, J = 1.9, 8.1 Hz), 8.43-8.50 (1H, m), 8.67(1H, dd, J = 1.6, 4.6 Hz), 8.95-8.98 (2H, m)

TABLE 23

¹H-NMR δ (ppm) 233 0.91 (3H, s), 1.26 (1H, s), 1.45 (3H, s), 1.70 (3H,s), 1.32-1.97 (29H, m), 2.14-2.19 (1H, m), 2.66-2.90 (3H, m), 3.06 (1H,s), 3.67 (1H, d, J = 11.9 Hz), 3.78 (1H, d, J = 11.9 Hz), 4.78 (1H, dd,J = 5.4, 10.8 Hz), 4.98-5.01 (2H, m), 6.40 (1H, s), 7.42 (1H, dd, J =4.9, 8.1 Hz), 8.11 (1H, dt, J = 1.6, 8.1 Hz), 8.69 (1H, d, J = 4.6 Hz),9.01 (1H, s) 234 0.91 (3H, s), 1.45 (3H, s), 1.70 (3H, s), 1.10-2.05(37H, m), 2.14-2.49 (3H, m), 3.04 (1H, s), 3.65 (1H, d, J = 11.3 Hz),3.77 (1H, d, J = 11.9 Hz), 4.78 (1H, dd, J = 5.4, 10.8 Hz), 4.97-5.01(2H, m), 6.41 (1H, s), 7.42 (1H, dd, J = 4.9, 8.1 Hz), 8.11 (1H, dd, J =1.9, 8.1 Hz), 8.69 (1H, d, J = 4.3 Hz), 9.01 (1H, s) 235 1.00 (3H, s),1.25-1.33 (3H, m), 1.48 (3H, s), 1.55 (1H, m), 1.71 (1H, m), 1.75 (3H,s), 1.79-1.98 (2H, m), 2.11-2.21 (1H, m), 3.48 (2H, s), 3.54 (2H, s),3.60 (2H, s), 3.90 (1H, d, J = 11.9 Hz), 3.99 (1H, d, J = 11.9 Hz), 4.86(1H, m), 4.98 (1H, m), 5.07-5.12 (1H, m), 6.53 (1H, s), 7.53 (1H, dd, J= 4.9, 8.1 Hz), 8.23 (1H, m), 8.30 (1H, m), 8.70 (1H, m), 9.05 (1H, m)236 0.11-0.27 (3H, m), 0.52-0.65 (8H, m), 0.88 (3H, s), 0.99-1.14 (5H,m), 1.15 (3H, s), 1.25-1.43 (2H, m), 1.61-1.76 (4H, m), 1.72 (3H, s),2.18-2.54 (9H, m), 3.74 (1H, d, J = 11.9 Hz), 3.83 (1H, d, J = 11.9 Hz),4.86 (1H, dd, J = 4.6, 11.6 Hz), 5.01-5.12 (2H, m), 6.41 (1H, s), 7.45(1H, dd, J = 4.9, 7.8 Hz), 8.16 (1H, m), 8.71 (1H, m), 9.02 (1H, s) 2370.14-0.26 (6H, m), 0.52-0.64 (6H, m), 0.92 (3H, s), 0.97-1.16 (4H, m),1.26-1.38 (1H, m), 1.45 (3H, s), 1.52 (1H, m), 1.63- 1.70 (2H, m), 1.70(3H, s), 1.82-1.91 (2H, m), 2.12-2.41 (7H, m), 2.96 (1H, m), 3.74 (1H,d, J = 11.9 Hz), 3.86 (1H, d, J = 11.9 Hz), 4.84 (1H, dd, J = 4.9, 11.3Hz), 5.00-5.03 (2H, m), 6.43 (1H, s), 7.42 (1H, dd, J = 4.6, 7.8 Hz),8.11 (1H, m), 8.70 (1H, d, J = 4.3 Hz), 9.01 (1H, s) 238 0.91 (3H, s),1.26 (1H, s), 1.44 (3H, s), 1.45 (3H, s), 1.46 (3H, s), 1.34-1.53 (7H,m), 1.52 (3H, s), 1.70 (3H, s), 1.81-2.02 (2H, m), 2.15-2.31 (3H, m),2.96 (1H, s), 3.67 (1H, m), 4.00 (1H, m), 4.85-5.00 (3H, m), 6.46 (1H,s), 7.45 (1H, dd, J = 4.9, 8.1 Hz), 8.13 (1H, m), 8.70 (1H, m), 9.02(1H, s) 239 0.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6Hz), 1.26 (1H, s), 1.33-1.44 (1H, m), 1.50 (3H, s), 1.61 (1H, m),1.68-1.77 (2H, m), 1.84 (3H, s), 1.91-1.99 (2H, m), 2.17-2.23 (1H, m),2.32 (2H, q, J = 7.6 Hz), 2.43 (2H, dq, J = 3.0, 7.6 Hz), 2.69 (3H, s),2.96 (1H, m), 3.75 (1H, d, J = 12.2 Hz), 3.80 (1H, d, J = 12.2 Hz), 4.48(1H, dd, J = 5.1, 11.1 Hz), 5.04 (1H, d, J = 4.1 Hz), 5.23 (1H, d, J =5.4, 10.8 Hz), 6.42 (1H, s), 7.24 (1H, d, J = 5.9 Hz), 7.39 (1H, dd, J =4.9, 8.1 Hz), 8.08 (1H, d, J = 8.4 Hz), 8.61 (1H, d, J = 5.1 Hz), 8.67(1H, d, J = 3.5 Hz), 8.98 (1H, s), 9.17 (1H, s)

TABLE 24

¹H-NMR δ (ppm) 240 0.93 (3H, s), 1.13 (3H, t, J = 7.9 Hz), 1.19 (3H, t,J = 7.9 Hz), 1.26 (1H, s), 1.39-1.43 (1H, m), 1.49 (3H, s), 1.61 (1H,m), 1.68-1.79 (2H, m), 1.82 (3H, s), 1.88-2.04 (2H, m), 2.17-2.23 (1H,m), 2.32 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 1.9, 7.6 Hz), 2.96 (1H,s), 3.74 (1H, d, J = 11.9 Hz), 3.83 (1H, d, J = 11.9 Hz), 4.83 (1H, dd,J = 1.6, 5.4 Hz), 5.04 (1H, d, J = 4.1 Hz), 5.27 (1H, dd, J = 5.4, 11.6Hz), 6.43 (1H, s), 7.39 (1H, dd, J = 4.9, 8.1 Hz), 7.47 (1H, d, J = 5.1Hz), 8.08 (1H, dt, J = 1.9, 8.1 Hz), 8.68 (1H, dd, J = 1.4, 4.6 Hz),8.64 (1H, d, J = 5.1 Hz), 8.99 (1H, d, J = 1.9 Hz), 9.14 (1H, s) 2410.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 7.6 Hz), 1.26(1H, s), 1.38-1.43 (1H, m), 1.49 (3H, s), 1.59 (1H, d, J = 4.4 Hz),1.66-1.73 (2H, m), 1.78 (3H, s), 1.82-2.05 (2H, m), 2.18-2.23 (1H, m),2.31 (2H, q, J = 7.6 Hz), 2.41 (2H, dq, J = 1.4, 7.6 Hz), 2.96 (1H, s),3.72 (1H, d, J = 7.6 Hz), 3.81 (1H, d, J = 7.6 Hz), 3.98 (3H, s), 4.84(1H, dd, J = 5.4, 11.3 Hz), 5.04 (1H, m), 5.24 (1H, dd, J = 4.9, 10.8Hz), 6.54 (1H, s), 7.39 (1H, dd, J = 4.9, 8.1 Hz), 7.53 (1H, d, J = 4.9Hz), 8.08 (1H, dt, J = 1.9, 8.1 Hz), 8.68 (1H, d, J = 4.1 Hz), 8.88 (1H,d, J = 4.9 Hz), 9.00 (1H, s), 9.17 (1H, s) 242 0.95 (3H, s), 1.15 (3H,t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 1.26 (1H, s), 1.38-1.44 (1H,m), 1.49 (3H, s), 1.61 (1H, d, J = 4.1 Hz), 1.68-1.72 (2H, m), 1.76 (3H,s), 1.82-2.06 (2H, m), 2.18-2.23 (1H, m), 2.34 (2H, q, J = 7.6 Hz), 2.43(2H, dq, J = 2.2, 7.6 Hz), 2.96 (1H, s), 3.78 (1H, d, J = 12.2 Hz), 3.83(1H, d, J = 12.2 Hz), 4.84 (1H, dd, J = 5.4, 11.3 Hz), 5.04 (1H, d, J =4.1 Hz), 5.2-5.23 (1H, m), 6.40 (1H, s), 7.40 (1H, dd, J = 4.9, 8.1 Hz),7.76 (1H, d, J = 5.4 Hz), 8.02-8.11 (2H, m), 8.69 (1H, d, J = 4.3 Hz),8.74 (1H, s), 9.00 (1H, s) 243 0.93 (3H, s), 1.14 (3H, t, J = 7.6 Hz),1.20 (3H, t, J = 7.6 Hz), 1.26 (1H, s), 1.39-1.44 (1H, m), 1.50 (3H, s),1.62 (1H, m), 1.68-1.75 (2H, m), 1.84 (3H, s), 1.93-1.96 (2H, m),2.14-2.23 (1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 2.4, 7.6Hz), 2.96 (1H, s), 3.72 (1H, d, J = 11.9 Hz), 3.83 (1H, d, J = 11.9 Hz),4.83 (1H, dd, J = 1.6, 5.4 Hz), 5.04 (1H, m), 5.36 (1H, dd, J = 4.9,11.3 Hz), 6.46 (1H, s), 7.38 (1H, dd, J = 5.4, 7.6 Hz), 7.68-7.78 (2H,m), 7.83-7.88 (1H, m), 8.07 (1H, dt, J = 1.9, 8.1 Hz), 8.19-8.23 (1H,m), 8.67 (1H, dd, J = 1.6, 4.9 Hz), 8.98 (1H, d, J = 2.2 Hz) 244 0.93(3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J = 7.6 Hz), 1.26 (1H,s), 1.34-1.43 (1H, m), 1.48 (3H, s), 1.60 (1H, d, J = 4.1 Hz), 1.66-2.02(4H, m), 1.73 (3H, s), 2.11-2.23 (1H, m), 2.33 (2H, q, J = 7.6 Hz), 2.41(2H, dq, J = 2.2, 7.6 Hz), 2.90 (1H, s), 3.74 (1H, d, J = 11.0 Hz), 5.83(1H, d, J = 11.9 Hz), 4.82 (1H, dd, J = 4.9, 11.1 Hz), 5.03 (1H, m),6.27 (1H, dd, J = 5.1, 11.6 Hz), 6.43 (1H, s), 7.41 (1H, dd, J = 4.9,8.1 Hz), 7.65-7.70 (2H, m), 7.78-7.86 (2H, m), 8.09 (1H, dt, J = 1.9,8.1 Hz), 8.69 (1H, d, J = 3.8 Hz), 9.00 (1H, s)

TABLE 25

¹H-NMR δ (ppm) 245 0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.20 (3H, t,J = 7.5 Hz), 1.26 (1H, s), 1.39-1.46 (1H, m), 1.49 (3H, s), 1.62 (1H, d,J = 4.1 Hz), 1.83 (3H, s), 1.66-2.02 (4H, m), 2.11-2.23 (1H, m), 2.33(2H, dq, J = 1.2, 7.6 Hz), 2.42 (2H, dq, J = 3.2, 7.6 Hz), 2.96 (1H, m),3.70 (1H, d, J = 12.0 Hz), 3.85 (1H, d, J = 12.0 Hz), 4.83 (1H, dd, J =4.9, 11.7 Hz), 5.04 (1H, m), 5.27 (1H, dd, J = 5.1, 11.9 Hz), 6.45 (1H,s), 7.18 (1H, dd, J = 8.5, 10.9 Hz), 7.27 (1H, m), 7.38 (1H, dd, J =4.8, 8.1 Hz), 7.55-7.61 (1H, m), 8.03 (1H, dt, J = 1.7, 7.3 Hz), 8.08(1H, dt, J = 1.7, 8.3 Hz), 8.67 (1H, d, J = 3.9 Hz), 8.98 (1H, s) 2460.93 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19 (3H, t, J = 7.5 Hz), 1.26(1H, s), 1.32-1.42 (1H, m), 1.45 (3H, s), 1.59 (1H, d, J = 3.0 Hz), 1.66(3H, s), 1.69-1.92 (4H, m), 2.02-2.21 (1H, m), 2.33 (2H, dq, J = 1.1,5.1 Hz), 2.42 (2H, dq, J = 2.2, 5.1 Hz), 2.96 (1H, m), 3.76 (1H, d, J =11.9 Hz), 3.84 (1H, d, J = 12.0 Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz),5.03 (1H, d, J = 4.2 Hz), 5.19 (1H, dd, J = 5.4, 11.7 Hz), 6.60 (1H, s),7.42 (1H, dd, J = 4.6, 8.1 Hz), 7.66-7.76 (2H, m), 7.84 (1H, dd, J =1.5, 7.5 Hz), 7.93 (1H, dd, J = 1.5, 7.8 Hz), 8.11 (1H, dt, J = 2.1, 8.1Hz), 8.69 (1H, d, J = 4.6 Hz), 9.03 (1H, s) 247 0.93 (3H, s), 1.14 (3H,t, J = 7.6 Hz), 1.20 (3H, t, J = 7.6 Hz), 1.26 (1H, s), 1.42-1.46 (1H,m), 1.49 (3H, s), 1.61 (1H, d, J = 3.0 Hz), 1.68-1.79 (2H, m), 1.82 (3H,s), 1.86-2.02 (2H, m), 2.16-2.22 (1H, m), 2.33 (2H, dq, J = 1.1, 5.1Hz), 2.42 (2H, dq, J = 2.4, 5.1 Hz), 2.96 (1H, m), 3.74 (1H, d, J = 12.0Hz), 3.82 (1H, d, J = 12.0 Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz), 5.04(1H, m), 5.27 (1H, dd, J = 5.1, 11.7 Hz), 6.44 (1H, s), 7.40 (1H, dd, J= 4.6, 7.8 Hz), 7.72 (1H, dd, J = 1.7, 8.3 Hz), 8.08 (1H, dt, J = 2.2,8.5 Hz), 8.26 (1H, dd, J = 1.9, 7.8 Hz), 8.58 (1H, dd, J = 1.9, 4.9 Hz),8.68 (1H, d, J = 3.6 Hz), 9.03 (1H, d, J = 1.7 Hz) 248 0.93 (3H, s),1.16 (3H, t, J = 7.6 Hz), 1.22 (3H, t, J = 7.6 Hz), 1.26 (1H, s),1.42-1.46 (1H, m), 1.49 (3H, s), 1.61 (1H, d, J = 3.0 Hz), 1.68-1.78(2H, m), 1.82 (3H, s), 1.86-2.01 (2H, m), 2.17-2.22 (1H, m), 2.33 (2H,dq, J = 1.1, 5.1 Hz), 2.42 (2H, dq, J = 2.4, 5.1 Hz), 2.62 (3H, s), 2.98(1H, m), 3.73 (1H, d, J = 12.0 Hz), 3.84 (1H, d, J = 11.9 Hz), 4.83 (1H,dd, J = 4.8, 11.5 Hz), 5.04 (1H, d, J = 3.4 Hz), 5.25 (1H, dd, J = 5.1,11.4 Hz), 6.44 (1H, s), 7.22 (1H, d, J = 7.8 Hz), 7.40 (1H, dd, J = 4.9,8.0 Hz), 8.08 (1H, dt, J = 2.2, 8.0 Hz), 8.18 (1H, d, J = 7.8 Hz), 8.69(1H, d, J = 3.7 Hz), 8.99 (1H, d, J = 1.7 Hz) 249 0.91 (3H, s), 1.14(3H, t, J = 7.8 Hz), 1.15 (3H, t, J = 7.8 Hz), 1.26 (1H, s), 1.29-1.39(1H, m), 1.42 (3H, s), 1.45 (1H, m), 1.57-1.64 (2H, m), 1.66 (3H, s),1.81-1.88 (2H, m), 2.14-2.18 (1H, m), 2.33 (2H, q, J = 7.8 Hz), 2.35(2H, q, J = 7.8 Hz), 2.84 (1H, m), 3.46 (3H, s), 3.68 (1H, d, J = 11.7Hz), 3.93 (1H, d, J = 11.9 Hz), 4.73-4.87 (4H, m), 4.95-5.00 (1H, m),6.43 (1H, s), 7.42 (1H, dd, J = 4.8, 8.0 Hz), 8.12 (1H, m), 8.69 (1H,m), 9.01 (1H, d, J = 2.2 Hz) 250 0.92 (3H, s), 1.26 (1H, s), 1.34-1.55(3H, m), 1.46 (3H, s), 1.71 (3H, s), 1.66-1.92 (6H, m), 2.01-2.18 (4H,m), 2.38- 2.57 (3H, m), 3.66-3.78 (1H, m), 3.95-4.13 (1H, m), 4.73- 4.84(1H, m), 4.89-4.95 (1H, m), 4.99-5.10 (1H, m), 6.45 (1H, s), 7.43 (1H,dd, J = 4.9, 8.3 Hz), 8.11 (1H, m), 8.70 (1H, d, J = 4.9 Hz), 9.02 (1H,s)

TABLE 26

¹H-NMR δ (ppm) 251 0.93 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.17 (3H, t,J = 7.5 Hz), 1.26 (1H, s), 1.36 (9H, s), 1.42 (1H, m), 1.47 (3H, s),1.62- 1.70 (3H, m), 1.75 (3H, s), 1.80-1.95 (2H, m), 2.07-2.21 (1H, m),2.32 (2H, dq, J = 1.5, 7.5 Hz), 2.40 (2H, dq, J = 3.9, 7.6 Hz), 2.96(1H, m), 3.69 (1H, d, J = 11.9 Hz), 3.87 (1H, d, J = 11.9 Hz), 4.83 (1H,dd, J = 4.9, 11.7 Hz), 5.04 (1H, m), 5.36 (1H, dd, J = 5.1, 11.7 Hz),6.53 (1H, s), 7.39-7.43 (1H, m), 7.98 (1H, dd, J = 1.7, 8.0 Hz), 8.02(1H, s), 8.10 (1H, dt, J = 1.7, 8.0 Hz), 8.65 (1H, dd, J = 1.5, 4.7 Hz),8.69 (1H, d, J = 3.7 Hz), 8.99 (1H, s) 252 0.92 (3H, s), 1.14 (3H, t, J= 7.5 Hz), 1.19 (3H, t, J = 7.5 Hz), 1.26 (1H, s), 1.42-1.45 (1H, m),1.49 (3H, s), 1.62-1.73 (3H, m), 1.82 (3H, s), 1.84-2.00 (2H, m),2.18-2.22 (1H, m), 2.32 (2H, dq, J = 1.5, 7.5 Hz), 2.41 (2H, dq, J =2.5, 7.5 Hz), 2.96 (1H, m), 3.68 (1H, d, J = 11.9 Hz), 3.85 (1H, d, J =11.9 Hz), 4.82 (1H, dd, J = 4.9, 11.7 Hz), 5.04 (1H, m), 5.37 (1H, dd, J= 4.8, 11.7 Hz), 6.44 (1H, s), 7.36-7.41 (2H, m), 8.08 (1H, dt, J = 1.7,8.0 Hz), 8.53 (1H, d, J = 2.0 Hz), 8.68 (1H, dd, J = 0.7, 4.9 Hz), 8.98(1H, d, J = 2.6 Hz) 253 0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.20(3H, t, J = 7.5 Hz), 1.26 (1H, s), 1.40-1.47 (1H, m), 1.51 (3H, s), 1.64(1H, d, J = 2.4 Hz), 1.73 (2H, m), 1.87 (3H, s), 1.85-2.00 (2H, m),2.18- 2.23 (1H, m), 2.32 (2H, q, J = 7.6 Hz), 2.42 (2H, dq, J = 1.5, 7.6Hz), 2.96 (1H, m), 3.71 (1H, d, J = 12.0 Hz), 3.83 (1H, d, J = 11.9 Hz),4.84 (1H, dd, J = 4.9, 11.7 Hz), 5.05 (1H, m), 5.39 (1H, dd, J = 5.2,11.6 Hz), 6.42 (1H, s), 7.39 (1H, dd, J = 4.9, 8.1 Hz), 8.02 (1H, s),8.07 (1H, m), 8.68 (1H, d, J = 4.4 Hz), 8.80-8.83 (1H, m), 8.97 (1H, m),9.38 (1H, m) 254 0.91 (3H, s), 1.14 (3H, t, J = 7.6 Hz), 1.19 (3H, t, J= 7.6 Hz), 1.26 (1H, s), 1.39-1.46 (1H, m), 1.49 (3H, s), 1.63 (1H, d, J= 2.7 Hz), 1.70-1.73 (2H, m), 1.85 (3H, s), 1.88-2.01 (2H, m), 2.18-2.22(1H, m), 2.32 (2H, q, J = 7.5 Hz), 2.41 (2H, dq, J = 2.2, 7.6 Hz), 2.97(1H, m), 3.68 (1H, d, J = 11.7 Hz), 3.83 (1H, d, J = 11.9 Hz), 4.83 (1H,dd, J = 4.9, 11.7 Hz), 5.04 (1H, m), 5.34 (1H, dd, J = 5.4, 11.5 Hz),6.44 (1H, s), 7.39 (1H, dd, J = 4.9, 8.0 Hz), 8.07 (1H, dt, J = 1.9, 6.3Hz), 8.32 (1H, d, J = 2.0 Hz), 8.67 (1H, d, J = 4.1 Hz), 8.92 (1H, d, J= 2.0 Hz), 8.98 (1H, s) 255 0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19(3H, t, J = 7.5 Hz), 1.26 (1H, s), 1.38-1.45 (1H, m), 1.49 (3H, s), 1.60(1H, d, J = 3.0 Hz), 1.68-1.70 (2H, m), 1.83 (3H, s), 1.75-1.98 (2H, m),2.17-2.21 (1H, m), 2.33 (2H, dq, J = 1.7, 7.5 Hz), 2.41 (2H, dq, J =2.2, 7.5 Hz), 2.97 (1H, m), 3.67 (1H, d, J = 12.0 Hz), 3.87 (1H, d, J =11.9 Hz), 4.81 (1H, dd, J = 4.9, 11.7 Hz), 5.03 (1H, m), 5.23 (1H, dd, J= 5.1, 11.5 Hz), 6.46 (1H, s), 7.07 (1H, d, J = 5.2 Hz), 7.39 (1H, dd, J= 4.9, 8.1 Hz), 7.54 (1H, d, J = 5.3 Hz), 8.08 (1H, dt, J = 2.2, 8.1Hz), 8.67 (1H, dd, J = 1.4, 4.9 Hz), 8.99 (1H, d, J = 2.2 Hz)

TABLE 27

¹H-NMR δ (ppm) 256 0.92 (3H, s), 1.12 (3H, t, J = 7.8 Hz), 1.16 (3H, t,J = 7.7 Hz), 1.26 (1H, s), 1.39-1.47 (1H, m), 1.50 (3H, s), 1.61 (1H, d,J = 2.4 Hz), 1.69-1.81 (2H, m), 1.85 (3H, s), 1.90-1.99 (2H, m),2.18-2.21 (1H, m), 2.33 (2H, dq, J = 1.2, 7.7 Hz), 2.41 (2H, dq, J =2.7, 7.6 Hz), 2.66 (3H, s), 2.96 (1H, m), 3.72 (1H, d, J = 11.7 Hz),3.83 (1H, d, J = 12.0 Hz), 4.83 (1H, dd, J = 4.9, 11.4 Hz), 5.04 (1H,m), 5.25 (1H, dd, J = 5.3, 11.7 Hz), 6.41 (1H, s), 7.30 (1H, d, J = 8.0Hz), 7.38 (1H, dd, J = 4.9, 8.1 Hz), 8.07 (1H, dt, J = 22, 8.1 Hz), 8.24(1H, dd, J = 2.2, 8.0 Hz), 8.67 (1H, dd, J = 1.5, 4.9 Hz), 8.97 (1H, d,J = 2.2 Hz), 9.18 (1H, d, J = 2.2 Hz) 257 0.91 (3H, s), 1.14 (3H, t, J =7.5 Hz), 1.19 (3H, t, J = 7.5 Hz), 1.26 (1H, s), 1.38-1.46 (1H, m), 1.50(3H, s), 1.63 (1H, d, J = 2.4 Hz), 1.70-1.73 (2H, m), 1.86 (3H, s),1.83-1.98 (2H, m), 2.18-2.22 (1H, m), 2.32 (2H, dq, J = 1.5, 7.7 Hz),2.41 (2H, dq, J = 2.2, 7.7 Hz), 2.96 (1H, d, J = 1.9 Hz), 3.68 (1H, d, J= 11.9 Hz), 3.84 (1H, d, J = 12.0 Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz),5.05 (1H, m), 5.32 (1H, dd, J = 5.3, 11.7 Hz), 6.43 ((1H, s), 7.39 1H,dd, J = 4.9, 8.0 Hz), 7.56 (1H, d, J = 8.1 Hz), 7.85 (1H, t, J = 7.8Hz), 8.07 (2H, m), 8.67 (1H, dd, J = 1.7, 4.9 Hz), 8.98 (1H, d, J = 2.0Hz) 258 0.91 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19 (3H, t, J = 7.5Hz), 1.26 (1H, s), 1.38-1.46 (1H, m), 1.50 (3H, s), 1.62 (1H, d, J = 2.4Hz), 1.69-1.72 (2H, m), 1.86 (3H, s), 1.80-1.96 (2H, m), 2.18-2.22 (1H,m), 2.32 (2H, q, J = 7.5 Hz), 2.41 (2H, dq, J = 2.2, 7.5 Hz), 2.93 (1H,d, J = 1.9 Hz), 3.68 (1H, d, J = 11.9 Hz), 3.83 (1H, d, J = 12.0 Hz),4.83 (1H, dd, J = 4.9, 11.4 Hz), 5.04 (1H, m), 5.33 (1H, dd, J = 5.3,11.5 Hz), 6.42 (1H, s), 7.20 (1H, dd, J = 2.9, 8.0 Hz), 7.38 (1H, dd, J= 4.9, 8.3 Hz), 8.00 (1H, q, J = 7.8 Hz), 8.08 (2H, m), 8.67 (1H, dd, J= 1.4, 4.6 Hz), 8.97 (1H, d, J = 2.2 Hz) 259 0.93 (3H, s), 1.14 (3H, t,J = 7.5 Hz), 1.21 (3H, t, J = 7.5 Hz), 1.26 (1H, s), 1.40-1.47 (1H, m),1.51 (3H, s), 1.61 (1H, d, J = 3.0 Hz), 1.70-1.83 (2H, m), 1.86 (3H, s),1.92-1.98 (2H, m), 2.17-2.22 (1H, m), 2.32 (2H, q, J = 7.3 Hz), 2.43(2H, dq, J = 1.4, 5.3 Hz), 2.97 (1H, d, J = 2.0 Hz), 3.74 (1H, d, J =11.7 Hz), 3.83 (1H, d, J = 11.7 Hz), 4.13 (3H, s), 4.84 (1H, dd, J =4.9, 11.4 Hz), 5.05 (1H, m), 5.24 (1H, dd, J = 5.3, 11.7 Hz), 6.43 (1H,s), 7.16-7.20 (1H, m), 7.35-7.44 (4H, m), 7.70 (1H, d, J = 8.1 Hz), 8.05(1H, dt, J = 1.7, 8.3 Hz), 8.66 (1H, dd, J = 1.5, 4.9 Hz), 8.96 (1H, d,J = 2.2 Hz) 260 0.93 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.19 (3H, t, J =7.5 Hz), 1.26 (1H, s), 1.40-1.46 (1H, m), 1.48 (3H, s), 1.63 (1H, d, J =3.0 Hz), 1.71-1.74 (2H, m), 1.80 (3H, s), 1.83-1.95 (1H, m), 2.02-2.06(1H, m), 2.18-2.22 (1H, m), 2.32 (2H, dq, J = 1.7, 7.6 Hz), 2.41 (2H,dq, J = 3.4, 7.5 Hz), 2.96 (1H, m), 3.70 (1H, d, J = 12.0 Hz), 3.87 (1H,d, J = 11.9 Hz), 4.83 (1H, dd, J = 4.8, 11.5 Hz), 5.05 (1H, m), 5.37(1H, dd, J = 4.9, 11.7 Hz), 6.46 (1H, s), 7.39-7.45 (2H, m), 7.87 (1H,dd, J = 1.5, 8.3 Hz), 8.08 (1H, dt, J = 1.5, 8.3 Hz), 8.64 (1H, dd, J =1.2, 4.6 Hz), 8.69 (1H, d, J = 4.9 Hz), 8.97 (1H, d, J = 2.2 Hz) 2610.85-1.06 (8H, m), 0.92 (3H, s), 1.26 (1H, s), 1.30-1.40 (1H, m), 1.42(3H, s), 1.45-1.63 (5H, m), 1.67 (3H, s), 1.81-1.92 (2H, m), 2.14-2.25(2H, m), 2.88 (1H, d, J = 1.4 Hz), 3.75 (1H, d, J = 11.9 Hz), 3.86 (1H,d, J = 11.6 Hz), 3.78-3.82 (1H, m), 4.82 (1H, dd, J = 5.1, 11.4 Hz),5.00 (1H, m), 6.52 (1H, s), 7.42 (1H, dd, J = 4.9, 8.0 Hz), 8.11 (1H,dt, J = 1.7, (8.0 Hz), 8.69 1H, dd, J = 1.5, 4.9 Hz), 9.01 (1H, d, J =1.9 Hz)

TABLE 28

¹H-NMR δ (ppm) 262 0.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.20 (3H, t,J = 7.5 Hz), 1.26 (1H, s), 1.39-1.47 (1H, m), 1.49 (3H, s), 1.61 (1H, d,J = 2.7 Hz), 1.66-1.71 (2H, m), 1.84 (3H, s), 1.76-1.99 (2H, m),2.18-2.22 (1H, m), 2.32 (2H, dq, J = 1.0, 7.5 Hz), 2.42 (2H, dq, J =2.7, 7.5 Hz), 2.96 (1H, m), 3.73 (1H, d, J = 11.9 Hz), 3.82 (1H, d, J =11.9 Hz), 4.83 (1H, dd, J = 4.9, 11.7 Hz), 5.04 (1H, m), 5.26 (1H, dd, J= 5.1, 11.7 Hz), 6.44 (1H, s), 7.35-7.41 (2H, m), 8.07 (1H, dt, J = 1.7,8.0 Hz), 8.44-8.50 (2H, m), 8.67 (1H, d, J = 4.9 Hz), 8.98 (1H, d, J =1.7 Hz) 263 0.92 (3H, s), 1.12 (3H, t, J = 7.5 Hz), 1.20 (3H, t, J = 7.5Hz), 1.26 (1H, s), 1.30-1.47 (1H, m), 1.50 (3H, s), 1.62 (1H, d, J = 2.4Hz), 1.69-1.71 (2H, m), 1.85 (3H, s), 1.75-1.97 (2H, m), 2.18-2.22 (1H,m), 2.33 (2H, dq, J = 0.9, 7.6 Hz), 2.42 (2H, dq, J = 2.4, 7.6 Hz), 2.98(1H, m), 3.73 (1H, d, J = 11.6 Hz), 3.81 (1H, d, J = 11.9 Hz), 4.84 (1H,dd, J = 4.9, 11.7 Hz), 5.06 (1H, m), 5.26 (1H, dd, J = 5.1, 11.5 Hz),6.40 (1H, s), 7.38 (1H, dd, J = 4.9, 8.0 Hz), 7.80 (2H, d, J = 8.8 Hz),8.06 (1H, dt, J = 1.7, 8.0 Hz), 8.21 (2H, d, J = 8.8 Hz), 8.67 (1H, dd,J = 1.5, 4.9 Hz), 8.96 (1H, d, J = 1.7 Hz) 264 0.92 (3H, s), 1.14 (3H,t, J = 7.5 Hz), 1.20 (3H, t, J = 7.5 Hz), 1.26 (1H, s), 1.39-1.47 (1H,m), 1.51 (3H, s), 1.62 (1H, d, J = 2.4 Hz), 1.68-1.82 (2H, m), 1.86 (3H,s), 1.93-2.01 (2H, m), 2.19-2.23 (1H, m), 2.32 (2H, dq, J = 1.0, 7.6Hz), 2.42 (2H, dq, J = 2.4, 7.5 Hz), 2.97 (1H, m), 3.73 (1H, d, J = 11.9Hz), 3.80 (1H, d, J = 11.9 Hz), 4.84 (1H, dd, J = 4.9, 11.7 Hz), 5.05(1H, m), 5.26 (1H, dd, J = 5.1, 11.5 Hz), 6.41 (1H, s), 7.38(1H, dd, J =4.1, 8.0 Hz), 7.65 (1H, m), 7.90 (1H, dt, J = 1.5, 7.8 Hz), 8.07 (1H,dt, J = 2.2, 8.0 Hz), 8.34 (1H, dt, J = 1.5, 7.8 Hz), 8.38 (1H, t, J =1.5 Hz), 8.67 (1H, dd, J = 1.5, 4.9 Hz), 8.96 (1H, d, J = 2.4 Hz) 2650.92 (3H, s), 1.14 (3H, t, J = 7.5 Hz), 1.21 (3H, t, J = 7.5 Hz), 1.26(1H, s), 1.39-1.48 (1H, m), 1.41 (3H, s), 1.63 (1H, d, J = 2.7 Hz),1.63-1.83 (2H, m), 1.86 (3H, s), 1.90-1.98 (2H, m), 2.18-2.23 (1H, m),2.33 (2H, q, J = 7.5 Hz), 2.43 (2H, dq, J = 2.5, 7.6 Hz), 2.97 (1H, m),3.72 (1H, d, J = 11.9 Hz), 3.82 (1H, d, J = 12.0 Hz), 4.84 (1H, dd, J =4.9, 11.4 Hz), 5.05 (1H, d, J =4.1 Hz), 5.28 (1H, dd, J = 5.1, 11.5 Hz),6.42 (1H, s), 7.38 (1H, dd, J = 4.9, 8.0 Hz), 7.65 (1H, t, J = 7.8 Hz),7.88 (1H, d, J = 7.8 Hz), 8.06 (1H, dt, J = 1.8, 8.0 Hz), 8.30 (1H, d, J= 8.1 Hz), 8.36 (1H, s), 8.67 (1H, dd, J = 1.5, 4.9 Hz), 8.97 (1H, d, J= 2.2 Hz) 266 0.89 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.14 (3H, t, J =7.6 Hz), 1.26 (1H, s), 1.33-1.37 (1H, m), 1.42 (3H, s), 1.46-1.55 (1H,m), 1.58 (3H, s), 1.60-1.70 (2H, m), 1.78-1.91 (2H, m), 2.13- 2.17 (1H,m), 2.32 (2H, dq, J = 1.7, 7.3 Hz), 2.35 (2H, q, J = 7.3 Hz), 2.89 (1H,m), 3.66 (1H, d, J = 11.4 Hz), 3.81 (1H, d, J = 12.0 Hz), 3.96 (2H, s),4.76-4.82 (1H, m), 4.98-5.06 (2H, m), 6.38 (1H, s), 7.17-7.25 (1H, m),7.36-7.46 (2H, m), 7.69- 7.73 (1H, m), 8.08-8.12 (1H, m), 8.60 (1H, dt,J = 1.0, 4.9 Hz), 8.70 (1H, dd, J = 1.7, 4.9 Hz), 9.00 (1H, d, J = 1.4Hz)

TABLE 29

1H-NMR δ (ppm) 267 0.89 (3H, s), 1.13 (3H, t, J = 7.6 Hz), 1.15 (3H, t,J = 7.6 Hz), 1.26 (1H, s), 1.43 (3H, s), 1.50 (3H, d, J = 3.0 Hz), 1.61(3H, s), 1.58-1.70 (2H, m), 1.75-1.93 (2H, m), 2.14-2.18 (1H, m), 2.32(2H, q, J = 7.6 Hz), 2.36 (2H, q, J = 7.6 Hz), 2.90 (1H, d, J = 1.9 Hz),3.70 (1H, d, J = 12.0 Hz), 3.74 (2H, s), 3.77 (1H, d, J = 11.9 Hz), 4.79(1H, dd, J = 4.9, 11.4 Hz), 4.96- 5.00 (2H, m), 6.37 (1H, s), 7.32 (1H,dd, J = 4.8, 7.6 Hz), 7.42 (1H, dd, J = 4.9, 8.1 Hz), 7.71 (1H, d, J =7.8 Hz), 8.12 (1H, dt, J = 1.9, 8.1 Hz), 8.57 (1H, dd, J = 1.6, 4.8 Hz),8.65 (1H, d, J = 1.9 Hz), 8.70 (1H, dd, J = 1.6, 4.7 Hz), 9.04 (1H, d, J= 4.2 Hz) 269 0.85-1.11 (8H, m), 0.93 (3H, s), 1.26 (1H, s), 1.39-1.47(1H, m), 1.50 (3H, s), 1.55-1.68 (5H, m), 1.87 (3H, s), 1.83-2.02 (2H,m), 2.17-2.22 (1H, m), 2.96 (1H, s), 3.79 (1H, d, J = 12.2 Hz), 3.83(1H, d, J = 12.1 Hz), 4.85 (1H, dd, J = 4.9, 11.5 Hz), 5.04 (1H, m),5.38 (1H, dd, J = 5.12, 11.6 Hz), 6.46 (1H, s), 7.38 (1H, dd, J = 4.8,8.2 Hz), 7.69-7.80 (2H, m), 7.87 (1H, m), 8.08 (1H, dt, J = 2.2, 8.0Hz), 8.22 (1H, dd, J = 1.7, 7.5 Hz), 8.67 (1H, dd, J = 1.5, 4.9 Hz),8.98 (1H, d, J = 2.4 Hz) 270 0.86-1.10 (8H, m), 0.94 (3H, s), 1.26 (1H,s), 1.38-1.46 (1H, m), 1.49 (3H, s), 1.57-1.69 (5H, m), 1.75 (3H, s),1.78-2.05 (2H, m), 2.18-2.21 (1H, m), 2.93 (1H, m), 3.80 (1H, d, J =11.9 Hz), 3.84 (1H, d, J = 11.9 Hz), 4.84 (1H, dd, J = 5.0, 11.6 Hz),5.04 (1H, m), 5.31 (1H, dd, J = 5.0, 11.8 Hz), 6.42 (1H, s), 7.40 (1H,dd, J = 4.9, 8.3 Hz), 7.70 (1H, d, J = 5.3 Hz), 8.09 (1H, dt, J = 1.7,8.1 Hz), 8.69 (1H, dd, J = 1.6, 4.7 Hz), 8.97 (1H, d, J = 5.1 Hz), 9.00(1H, d, J = 2.2 Hz), 9.17 (1H, s) 271 0.85-1.08 (8H, m), 0.92 (3H, s),1.26 (1H, s), 1.38-1.46 (1H, m), 1.48 (3H, s), 1.56-1.68 (5H, m), 1.79(3H, s), 1.83-2.08 (2H, m), 2.18-2.21 (1H, m), 2.95 (1H, m), 3.76 (1H,d, J = 11.9 Hz), 3.86 (1H, d, J = 11.9 Hz), 4.83 (1H, dd, J = 4.9, 11.5Hz), 5.04 (1H, m), 5.39 (1H, dd, J = 5.1, 11.9 Hz), 646 (1H, s),7.34-7.45 (2H, m), 7.86 (1H, dd, J = 1.3, 8.0 Hz), 8.08 (1H, dt, J =2.0, 8.0 Hz), 8.64 (1H, dd, J = 1.2, 4.7 Hz), 8.68 (1H, dd, J = 1.5, 4.9Hz), 9.00 (1H, d, J = 2.2 Hz)

Example 11

Preparation Example 1 [Wettable Powder]

Compound according to the present invention

(Compound No. 82) 30 wt % Clay 30 wt % Diatomaceous earth 35 wt %Calcium lignin sulfonate  4 wt % Sodium laurylsulfate  1 wt %The above ingredients were homogeneously mixed together, and the mixturewas ground to prepare wettable powder.

Preparation Example 2 [Dust]

Compound according to the present invention

(Compound No. 82)  2 wt % Clay 60 wt % Talc 37 wt % Calcium stearate  1wt %The above ingredients were homogeneously mixed together to prepare dust.

Preparation Example 3 [Emulsifiable Concentrate]

Compound according to the present invention

(Compound No. 82) 20 wt % N,N-Dimethylformamide 20 wt % Solvesso 150(Exxon Mobil Corporation) 50 wt % Polyoxyethylene alkylaryl ether 10 wt%The above ingredients were homogeneously mixed and dissolved to prepareemulsifiable concentrate.

Preparation Example 4 [Granules]

Compound according to the present invention

(Compound No. 28)  5 wt % Bentonite 40 wt % Talc 10 wt % Clay 43 wt %Calcium lignin sulfonate  2 wt %The above ingredients were homogeneously ground and homogeneously mixedtogether. Water was added to the mixture, followed by thorough kneading.Thereafter, the kneaded product was granulated and dried to preparegranules.

Preparation Example 5 [Floables]

Compound according to the present invention (Compound No. 28) 25 wt %POE polystyrylphenyl ether sulfate 5 wt % Propylene glycol 6 wt %Bentonite 1 wt % 1% aqueous xanthan gum solution 3 wt % PRONAL EX-3000.05 wt % (Toho Chemical Industry Co. Ltd.) ADDAC 827 0.02 wt % (K.I.Chemical Industry Co., Ltd.) Water To 100 wt %All the above ingredients except for the 1% aqueous xanthan gum solutionand a suitable amount of water were premixed together, and the mixturewas then ground by a wet grinding mill. Thereafter, the 1% aqueousxanthan gum solution and the remaining water were added to the groundproduct to prepare 100 wt % floables.

Test Example 1 Pesticidal Effect Against Myzus persicae

Among the compounds of formula (I) produced by the conventional methoddescribed above, the compounds shown in Tables 1 to 14 and pyripyropeneA were tested for pesticidal effect.

A leaf disk having a diameter of 2.8 cmφ was cut out from a cabbagegrown in a pot and was placed in a 5.0 cm-Schale. Four adult aphids ofMyzus persicae were released in the Schale. One day after the release ofthe adult aphids, the adult aphids were removed. The number of larvae atthe first instar born in the leaf disk was adjusted to 10, and a testsolution, which had been adjusted to a concentration of 20 ppm by theaddition of a 50% aqueous acetone solution (0.05% Tween 20 added) wasspread over the cabbage leaf disk. The cabbage leaf disk was then airdried. Thereafter, the Schale was lidded and was allowed to stand in atemperature-controlled room (light period 16 hr-dark period 8 hr) (25°C.). Three days after the initiation of standing of the Schale, thelarvae were observed for survival or death, and the death rate of larvaewas calculated by the following equation.

Death rate (%)={number of dead larvae/(number of survived larvae+numberof dead larvae)}×100

As result, it was found that the death rate was not less than 80% forcompounds of Nos. 1, 6, 8, 9, 10, 12, 14, 16, 18, 20, 23, 25, 28, 34,35, 36, 37, 38, 39, 40, 44, 45, 49, 54, 56, 57, 61, 69, 76, 82, 85, 86,88, 90, 91, 98, 103, 106, 107, 108, 109, 111, 125, 128, 133, 135, 137,139, 142, 153, 160, 161, 162, 164, 167, 169, 170, 171, 172, 176, 180,182, 183, 186, 187, 190, 196, 201, 205, 206, 207, 208, 209, 210, 211,212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 226, 227,228, 229, 230, 231, 232, 233, 236, 237, 239, 240, 241, 242, 243, 244,245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 256, 257, 258,259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272,273, and 274 and pyripyropene A.

Test Example 2 Pesticidal Effect Against Myzus persicae

Among the compounds of formula (I) produced by the conventional methoddescribed above, the compounds shown in Tables 1 to 14 and pyripyropeneA were tested for pesticidal effect. A leaf disk having a diameter of2.8 cmφ was cut out from a cabbage grown in a pot and was placed in a5.0 cm-Schale. Four adult aphids of Myzus persicae were released in theSchale. One day after the release of the adult aphids, the adult aphidswere removed. The number of larvae at the first instar born in the leafdisk was adjusted to 10, and a test solution, which had been adjusted toa concentration of 0.156 ppm by the addition of a 50% aqueous acetonesolution (0.05% Tween 20 added) was spread over the cabbage leaf disk.The cabbage leaf disk was then air dried. Thereafter, the Schale waslidded and was allowed to stand in a temperature-controlled room (lightperiod 16 hr-dark period 8 hr) (25° C.). Three days after the initiationof standing, the larvae were observed for survival or death, and thedeath rate of larvae was calculated in the same manner as in TestExample 1.

As a result, it was found that the death rate was not less than 80% forcompounds of Nos. 12, 23, 28, 45, 54, 56, 76, 82, 85, 86, 90, 164, 201,205, 206, 207, 212, 213, 217, 218, 219, 222, 227, 228, 229, 231, 232,233, 237, 239, 240, 242, 246, 247, 249, 250, 252, 253, 256, 258, 261,262, 264, 265, 266, 267, 269, 270, and 271.

Test Example 3 Pesticidal Effect Against Plutella xylostella

A cabbage leaf disk having a diameter of 5 cm was placed in a plasticcup. Test compounds, which had been diluted to a predeterminedconcentration by the addition of a 50% aqueous acetone solution (Tween20, 0.05% added), were spreaded over the cabbage leaf disk by means of aspray gun, and the cabbage leaf disk was then air dried. Five larvae atthe second instar of Plutella xylostella were released in the cup. Thecup was then lidded, and the larvae were reared in thetemperature-controlled room (25° C.). Three days after the treatment,the larvae were observed for survival or death, and the death rate ofthe larvae was calculated in the same manner as in Test Example 1.

As a results, it was found that the death rate was not less than 80% forcompounds of Nos. 76, 213, 218, 237 and 250 at a concentration of 500ppm.

Test Example 4 Pesticidal Effect Against Helicoverpa armigera

A cabbage leaf disk having a diameter of 2.8 cm was placed in a plasticcup. Test compounds, which had been diluted to a predeterminedconcentration by the addition of a 50% aqueous acetone solution (Tween20, 0.05% added), were spreaded over the cabbage leaf disk by means of aspray gun, and the cabbage leaf disk was then air dried. A larva at thethird instar of Helicoverpa armigera was released in the cup. The cupwas then lidded, and the larva was reared in the temperature-controlledroom (25° C.). Three days after the treatment, the larva was observedfor survival or death. The test was repeated 5 times. Further, the deathrate of the larvae were calculated in the same manner as in Test Example1.

As a result, it was found that the death rate was not less than 80% forthe compound of No. 219 at a concentration of 100 ppm.

Test Example 5 Pesticidal Effect Against Trigonotylus caelestialium

A wheat seedling was immersed for 30 seconds in a solution, in whicheach test compound had been diluted to a predetermined concentration bythe addition of a 50% aqueous acetone solution (Tween 20, 0.05% added).The wheat seedling was air dried, and then placed in a glass cylinder.Further, two larvae at the second instar of Trigonotylus caelestialiumwere released in the glass cylinder. The glass cylinder was then lidded,and the larvae were reared in the temperature-controlled room (25° C.).During the test, the wheat seedling was supplied with water from thebottom of the glass cylinder. Three days after the treatment, the larvaewere observed for survival or death, and the death rate of the larvaewere calculated in the same manner as in Test Example 1.

As a result, it was found that the death rate was not less than 80% forcompound of Nos. 218 and 281 at a concentration of 100 ppm.

1. A composition for use as a pest control agent, comprising a compoundrepresented by formula (I) or an agriculturally and horticulturallyacceptable salt thereof as active ingredient and an agriculturally andhorticulturally acceptable carrier:

Het₁ represents optionally substituted 3-pyridyl R₁ represents hydroxyloptionally substituted C₁₋₆ alkylcarbonyloxy, optionally substitutedC₂₋₆ alkenylcarbonyloxy, optionally substituted C₂₋₆ alkynylcarbonyloxy,optionally substituted C₁₋₆ alkyloxy, optionally substituted C₂₋₆alkenyloxy, optionally substituted C₂₋₆ alkynyloxy, optionallysubstituted benzyloxy, or oxo in the absence of a hydrogen atom at the13-position, or the bond between 5-position and 13-position represents adouble bond in the absence of R₁ and a hydrogen atom at the 5-position,R₂ represents hydroxyl, optionally substituted C₁₋₁₈ alkylcarbonyloxy,optionally substituted C₂₋₆ alkenylcarbonyloxy, optionally substitutedC₂₋₆ alkynylcarbonyloxy, optionally substituted benzoyloxy, oroptionally substituted C₁₋₆ alkylsulfonyloxy, R₃ represents a hydrogenatom, hydroxyl, optionally substituted C₁₋₁₈ alkylcarbonyloxy,optionally substituted C₂₋₆ alkynylcarbonyloxy, optionally substitutedC₂₋₆ alkynylcarbonyloxy, optionally substituted benzoyloxy, optionallysubstituted C₁₋₆ alkylsulfonyloxy, optionally substitutedbenzenesulfonyloxy, or optionally substituted five- or six-memberedheterocyclic thiocarbonyloxy, or R₂ and R₃ together represent—O—CR₂′R₃′—O— wherein R₂′ and R₃′, which may be the same or different,represent a hydrogen atom, C₁₋₆ alkyl, C₁₋₆ alkyloxy, C₂₋₆ alkenyl,optionally substituted phenyl, or optionally substituted benzyl, or R₂′and R₃′ together represent oxo or C₂₋₆ alkylene, and R₄ represents ahydrogen atom, hydroxyl, optionally substituted C₁₋₁₈ alkylcarbonyloxy,optionally substituted C₂₋₆ alkenylcarbonyloxy, optionally substitutedC₂₋₆ alkynylcarbonyloxy, optionally substituted benzoyloxy, optionallysubstituted C₁₋₆ alkylsulfonyloxy, optionally substitutedbenzenesulfonyloxy, optionally substituted benzyloxy, optionallysubstituted C₁₋₆ alkyloxy, optionally substituted C₂₋₆ alkenyloxy,optionally substituted C₂₋₆ alkynyloxy, C₁₋₆ alkyloxy-C₁₋₆ alkyloxy,C₁₋₆ alkylthio-C₁₋₆ alkyloxy, C₁₋₆ alkyloxy-C₁₋₆ alkyloxy-C₁₋₆ alkyloxy,optionally substituted C₁₋₆ alkyloxycarbonyloxy, optionally substitutedC₁₋₆ alkylaminocarbonyloxy, optionally substituted saturated orunsaturated five- or six-membered heterocyclic oxy, optionallysubstituted saturated or unsaturated five- or six-membered heterocycliccarbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy,optionally substituted optionally substituted 1H-indolylcarbonyloxy,optionally substituted saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atomat the 7-position, provided that a compound wherein Het₁ represents3-pyridyl, R₁ represents hydroxyl, and all of R₂, R₃, and R₄ representacetyloxy, is excluded.
 2. The composition according to claim 1, whereinHet₁ represents 3-pyridyl, R₁ represents hydroxyl or C₁₋₆alkylcarbonyloxy. or the bond between 5-position and 13-positionrepresents a double bond in the absence of R₁ and a hydrogen atom at the5-position, R₂ represents optionally substituted C₁₋₆ alkylcarbonyloxy,R₃ represents optionally substituted C₁₋₆ alkylcarbonyloxy or C₁₋₆alkylsulfonyloxy, or R₂ and R₃ together represent —O—CR₂′R₃′—O— whereinR₂′ and R₃′, which may be the same or different, represent a hydrogenatom, C₁₋₆ alkyl, or optionally substituted phenyl, or R₂′ and R₃′together represent oxo or C₂₋₆ alkylene, and R₄ represents hydroxyl,optionally substituted C₁₋₆ alkylcarbonyloxy, saturated or unsaturatedfive- or six-membered heterocyclic oxy, optionally substitutedbenzoyloxy, C₁₋₃ alkyloxy-C₁₋₃ alkyloxy, optionally substituted C₁₋₆alkylaminocarbonyloxy, optionally substituted saturated or unsaturatedfive- or six-membered heterocyclic carbonyloxy, optionally substitutedthieno[3,2-b]pyridylcarbonyloxy, optionally substituted1H-indolylcarbonyloxy, saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atomat the 7-position.
 3. The composition according to claim 1, wherein Het₁represents 3-pyridyl, R₁ represents hydroxyl, R₂ represents optionallysubstituted C₁₋₆ alkylcarbonyloxy, and R₃ represents optionallysubstituted C₁₋₆ alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, and R₄represents hydroxyl, optionally substituted C₁₋₆ alkylcarbonyloxy,saturated or unsaturated five- or six-membered heterocyclic oxy,optionally substituted benzoyloxy, C₁₋₃ alkyloxy-C₁₋₃ alkyloxy,optionally substituted C₁₋₆ alkylaminocarbonyloxy, optionallysubstituted saturated or unsaturated five- or six-membered heterocycliccarbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy,optionally substituted 1H-indolylcarbonyloxy, saturated or unsaturatedfive- or six-membered heterocyclic thiocarbonyloxy, or oxo in theabsence of a hydrogen atom at the 7-position.
 4. The compositionaccording to claim 1, wherein Het₁ represents 3-pyridyl, R₁ representshydroxyl, R₂ represents optionally substituted C₁₋₆ alkylcarbonyloxy, R₃represents optionally substituted C₁₋₆ alkylcarbonyloxy or C₁₋₆alkylsulfonyloxy, and R₄ represents hydroxyl, optionally substitutedC₁₋₆ alkylcarbonyloxy, saturated or unsaturated five- or six-memberedheterocyclic oxy, optionally substituted benzoyloxy, optionallysubstituted saturated or unsaturated five- or six-membered heterocycliccarbonyloxy, or saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy.
 5. The composition according to claim 1,wherein Het₁ represents 3-pyridyl, R₁ represents hydroxyl, and R₂ and R₃represent optionally substituted cyclic C₃₋₆ alkylcarbonyloxy.
 6. Acomposition for use as a pest control agent, comprising a compoundrepresented by formula (Ia) or an agriculturally and horticulturallyacceptable salt thereof as active ingredient and an agriculturally andhorticulturally acceptable carrier:

wherein Het₂ represents optionally substituted 3-pyridyl, R₁₁ representshydroxyl, optionally substituted C₁₋₆ alkylcarbonyloxy, optionallysubstituted C₂₋₆ alkenylcarbonyloxy, optionally substituted C₂₋₆alkynylcarbonyloxy, optionally substituted C₁₋₆ alkyloxy, optionallysubstituted C₂₋₆ alkenyloxy, optionally substituted C₂₋₆ alkynyloxy,optionally substituted benzyloxy, or oxo in the absence of a hydrogenatom at the 13-position, or the bond between 5-position and 13-positionrepresents a double bond in the absence of R₁₁ and a hydrogen atom atthe 5-position, R₁₂ represents hydroxyl, optionally substituted C₁₋₁₈alkylcarbonyloxy, optionally substituted C₂₋₆ alkenylcarbonyloxy,optionally substituted C₂₋₆ alkynylcarbonyloxy, optionally substitutedbenzoyloxy, or optionally substituted C₁₋₆ alkylsulfonyloxy, R₁₃represents a hydrogen atom, hydroxyl, optionally substituted C₁₋₁₈alkylcarbonyloxy, optionally substituted C₂₋₆ alkenylcarbonyloxy,optionally substituted C₂₋₆ alkynylcarbonyloxy, optionally substitutedbenzoyloxy, optionally substituted C₁₋₆ alkylsulfonyloxy, optionallysubstituted benzenesulfonyloxy, or optionally substituted five- orsix-membered heterocyclic thiocarbonyloxy, or R₁₂ and R₁₃ togetherrepresent —O—CF₁₂′R₁₃′—O— wherein R₁₂′ and R₁₃′, which may be the sameor different, represents a hydrogen atom, C₁₋₆ alkyl, C₁₋₆ alkoxy, C₂₋₆alkenyl, optionally substituted phenyl, or optionally substitutedbenzyl, or R₁₂′ and R₁₃′ together represent oxo or C₂₋₆ alkylene, andR₁₄ represents a hydrogen atom, hydroxyl, optionally substituted C₁₋₁₈alkylcarbonyloxy, optionally substituted C₂₋₆ alkenylcarbonyloxy,optionally substituted C₂₋₆ alkynylcarbonyloxy, optionally substitutedbenzoyloxy, optionally substituted C₁₋₆ alkylsulfonyloxy, optionallysubstituted benzenesulfonyloxy, optionally substituted benzyloxy,optionally substituted C₁₋₆ alkyloxy, optionally substituted C₂₋₆alkenyloxy, optionally substituted C₂₋₆ alkynyloxy, C₁₋₆ alkyloxy-C₁₋₆alkyloxy, C₁₋₆ alkylthio-C₁₋₆ alkyloxy, C₁₋₆ alkyloxy-C₁₋₆ alkyloxy-C₁₋₆alkyloxy, optionally substituted C₁₋₆ alkyloxycarbonyloxy, optionallysubstituted C₁₋₆ alkylaminocarbonyloxy, optionally substituted saturatedor unsaturated five- or six-membered heterocyclic oxy, optionallysubstituted saturated or unsaturated five- or six-membered heterocycliccarbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy,optionally substituted 1H-indolylcarbonyloxy, optionally substitutedsaturated or unsaturated five- or six-membered heterocyclicthiocarbonyloxy, or oxo in the absence of a hydrogen atom at the7-position,
 7. The composition according to claim 8, wherein Het₂represents 3-pyridyl, R₁₁ represents hydroxyl or C₁₋₆ alkylcarbonyloxy,or the bond between 5-position and 13-position represents a double bondin the absence of R11 and a hydrogen atom at the 5-position, R₁₂represents optionally substituted C₁₋₆ alkylcarbonyloxy, R₁₃ representsoptionally substituted C₁₋₆ alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy,or R₁₂ and R₁₃ together represent —O—CR₁₂′R₁₃′—O— wherein R₁₂′ and R₁₃′,which may be the same or different, represent a hydrogen atom, C₁₋₆alkyl, or optionally substituted phenyl, or R₁₂′ and R₁₃′ togetherrepresent oxo or C₂₋₆ alkylene, and R₁₄ represents hydroxyl, optionallysubstituted C₁₋₆ alkylcarbonyloxy, saturated or unsaturated five- orsix-membered heterocyclic oxy, optionally substituted benzoyloxy, C₁₋₃alkyloxy-C₁₋₃ alkyloxy, optionally substituted C₁₋₆alkylaminocarbonyloxy, optionally substituted saturated or unsaturatedfive- or six-membered heterocyclic carbonyloxy, optionally substitutedthieno[3,2-b]pyridylcarbonyloxy, optionally substituted1H-indolylcarbonyloxy, saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy, or oxo in the absence of a hydrogen atomat the 7-position.
 8. The composition according to claim 8, wherein Het₂represents 3-pyridyl, R₁₁ represents hydroxyl, R₁₂ represents optionallysubstituted C₁₋₆ alkylcarbonyloxy, and R₁₃ represents optionallysubstituted C₁₋₆ alkylcarbonyloxy or C₁₋₆ alkylsulfonyloxy, and R₁₄represents hydroxyl, optionally substituted C₁₋₆ alkylcarbonyloxy,saturated or unsaturated five- or six-membered heterocyclic oxy,optionally substituted benzoyloxy, C₁₋₆ alkyloxy-C₁₋₃ alkyloxy,optionally substituted C₁₋₆ alkylaminocarbonyloxy, optionallysubstituted saturated or unsaturated five- or six- membered heterocycliccarbonyloxy, optionally substituted thieno[3,2-b]pyridylcarbonyloxy,optionally substituted 1-H-indolylcarbonyloxy, saturated or unsaturatedfive- or six-membered heterocyclic thiocarbonyloxy, or oxo in theabsence of a hydrogen atom at the 7-position.
 9. The compositionaccording to claim 6, wherein Het₂ represents 3-pyridyl, R₁₁ representshydroxyl, R₁₂ represents optionally substituted C₁₋₆ alkylcarbonyloxy,R₁₃ represents optionally substituted C₁₋₆ alkylcarbonyloxy or C₁₋₆alkylsulfonyloxy, and R₁₄ represents hydroxyl, optionally substitutedC₁₋₆ alkylcarbonyloxy, saturated or unsaturated five- or six-memberedheterocyclic oxy, optionally substituted benzoyloxy, optionallysubstituted saturated or unsaturated five- or six-membered heterocycliccarbonyloxy, or saturated or unsaturated five- or six-memberedheterocyclic thiocarbonyloxy.
 10. The composition according to claim 6,wherein Het₂ represents 3-pyridyl, R₁₁ represents hydroxyl, and R₁₂ andR₁₃ represent optionally substituted cyclic C₃₋₆ alkylcarbonyloxy. 11.The composition according to claim 6, wherein said hemipteran pest isselected from Aphidoidea, Coccoidea, or Aleyrodidae.
 12. The compositionaccording to claim 8, wherein said hemipteran pest is at least one pestselected from the group consisting of Myzus persicae, Aphis gossypii,Aphis fabae, Aphis maidis (corn-leaf aphid), Acyrthosiphon pisum,Aulacorthum solani, Aphis craccivora, Macrosiphum euphorbiae,Maerosiphum avenae, Metopolophium dirhodum, Rhopalosiphum padi,Schizaphis graminum, Brevicoryne brassicae, Lipaphis erysimi, Aphiscitricola, Rosy apple aphid, Eriosoma lanigerum, Toxoptera aurantii,Toxoptera citricidus, and Pseudoeoccus comstocki.
 13. A compoundrepresented by formula (Ib) or an agriculturally and horticulturallyacceptable salt thereof:

wherein Het₁ represents 3-pyridyl, R₁ represents hydroxyl, R₂ and R₃represent propionyloxy or optionally substituted cyclic C₃₋₆alkylcarbonyloxy, and R₄ represents hydroxyl, optionally substitutedcyclic C₃₋₆ alkylcarbonyloxy, optionally substituted benzoyloxy, oroptionally substituted saturated or unsaturated five- or six-memberedheterocyclic carbonyloxy, provided that a compound wherein Het₁represents 3-pyridyl, R₁ represents hydroxyl, R₂ and R₃ representpropionyloxy, and R₄ represents hydroxyl, is excluded.
 14. The compoundaccording to claim 13 or an agriculturally and horticulturallyacceptable salt thereof, wherein R₂ and R₃ represent optionallysubstituted cyclic C₃₋₆ alkylcarbonyloxy, and R₄ represents hydroxyl,optionally substituted cyclic C₃₋₆ alkylcarbonyloxy, or optionallysubstituted benzoyloxy.
 15. The compound according to claim 13 or anagriculturally and horticulturally acceptable salt thereof, wherein R₂and R₃ represent propionyloxy, and R₄ represents optionally substitutedcyclic C₃₋₆ alkylcarbonyloxy or optionally substituted saturated orunsaturated five- or six-membered heterocyclic carbonyloxy.
 16. Acomposition for use as a pest control agent comprising the compoundaccenting to claim 13 or an agriculturally and horticulturallyacceptable salt thereof as active ingredient and an agriculturally andhorticulturally acceptable carrier.
 17. A method for controlling a pest,comprising applying an effective amount of a compound represented byformula (I) according to claim 1 or an agriculturally andhorticulturally acceptable salt thereof to a plant or soil.
 18. A methodfor controlling a hemipteran pest, comprising applying an effectiveamount of a compound represented by formula (Ia) according to claim 6 oran agriculturally and horticulturally acceptable salt thereof to a plantor soil.
 19. A method for controlling an pest, comprising applying aneffective amount of a compound represented by formula (Ib) according toclaim 13 or an agriculturally and horticulturally acceptable saltthereof to a plant or soil.